KR100436518B1 - Hydrogenated ring-opening metathesis copolymer and process for producing the same - Google Patents

Abstract

The present invention is a ring-opening metathesis polymer-hydrogen additive comprising at least structural unit [B] represented by the following general formula [3] and / or structural unit [C] represented by the following general formula [4]:

[Wherein, R⁸-R¹¹And R¹³-R¹⁶Each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, X²And X³May be the same or different, and -O- or -CR¹² ₂-(R¹²Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. Y^OneAnd Y²Is-(C = 0)-on one side and -CR on the other side¹⁸ ₂-(R¹⁸Is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. m and n represent 0 or an integer of 1-3.

Description

Hydrocyclic Metathesis Copolymer Hydrogen Additives and Manufacturing Method {HYDROGENATED RING-OPENING METATHESIS COPOLYMER AND PROCESS FOR PRODUCING THE SAME}

In recent years, semiconductor integrated circuits have been integrated, and large-scale integrated circuits (LSIs) and ultra-large scale integrated circuits (VLSIs) have been put into practical use, and at the same time, the minimum lithography pattern of the integrated circuits reaches the sub-micron region, and further refines in the future. Tend to. To form the fine pattern, the substrate on which the thin film is formed is coated with a resist material, and subjected to selective exposure to form a latent image of a desired pattern, which is then developed to form a resist pattern, which is then subjected to dry etching. It is essential to use a lithographic technique in which the desired pattern is obtained by removing the resist material after that.

Ultraviolet light of g line (wavelength: 436 nm) and i line (wavelength: 365 nm) is used as the exposure light source used in this lithography technique. However, according to the microlithography of the pattern, ultraviolet light having a shorter wavelength, Vacuum ultraviolet light, electron beam (EB), X-rays and the like have come to be widely used as light sources. In particular, in recent years, an excimer laser (a KrF laser having a wavelength of 248 nm and an ArF laser having a wavelength of 193 nm) has been attracting attention as an exposure light source, and is expected to be effective for forming a microlithography pattern.

As a polymer or a copolymer used for the resist material which forms a submicron pattern using the exposure light of a shorter wavelength of the ultraviolet-ultraviolet region, acrylic acid which has a protecting group detached by an adamantane skeleton and an acid in an ester part, for example is used. Polymers or copolymers of esters or α-substituted acrylic acid esters (see Japanese Patent Application Laid-Open No. 4-39665), polymers of acrylic acid esters or α-substituted acrylic acid esters having a protecting group detached by an norbornane skeleton and an acid in the ester moiety or A copolymer (see Japanese Patent Application Laid-Open No. 5-257281), a polymer or copolymer of cyclohexyl maleimide (see Japanese Patent Application Laid-Open No. 5-257285), and a cellulose skeleton in the main chain, so that the main chain Macromolecular compounds causing cleavage (see Japanese Patent Application Laid-Open No. 6-342212) and polyvinyl alcohol or its poly Derivatives of polyvinyl alcohol (refer to Japanese Unexamined Patent Publication No. 7-333850) have been proposed a number of polymers and copolymers and the like.

However, it satisfies all the properties necessary for use as resist materials, such as dry etching resistance, transparency to far ultraviolet rays, solubility in resist solvents, wettability in developing solutions, adhesion to substrates such as silicon and solubility in release agents, Further, there are no polymers and copolymers that can be easily synthesized, and further development is required.

On the other hand, a photoresist composition composed of a polymer compound having an alicyclic hydrocarbon as a main chain and having a cyclic skeleton having a pendant group decomposed by an acid (WO 97/33198, Japanese Patent Laid-Open No. 09-230595, As shown in Japanese Patent Application Laid-Open No. 09-244247 and Japanese Patent Application Laid-open No. 10-254139, the cyclic polymer has excellent dry etching resistance and transparency to far ultraviolet rays, but has a high concentration of a resist solvent. There are problems such as solubility in water, wettability in developing solution and poor adhesion to silicon substrate.

The present invention relates to a novel ring-opening metathesis polymer hydrogenated material, and is also used for semiconductor microfabrication using ultraviolet rays or far ultraviolet rays (including excimer lasers, etc.) having excellent heat resistance, thermal decomposition resistance, and light transmittance. The present invention relates to a ring-opening metathesis polymer hydrogenated compound suitable for a base polymer for resist, and also to a method for producing such polymer hydrogenated product.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the ¹ H-NMR spectrum (270 MHz, in which the solvent is deuterated chloroform) of the ring-opened metathesis polymer hydrogenated product obtained in Example 1;

SUMMARY OF THE INVENTION An object of the present invention is for semiconductor microfabrication using the above-mentioned various performances required for use as a base polymer for resist materials, specifically, ultraviolet rays or far ultraviolet rays (including excimer lasers, etc.). It satisfies all of the various performances necessary for use as a base polymer for resist materials in positive photoresist compositions which have high sensitivity, high resolution, high affinity for alkaline developing solutions, and a good pattern. It is to provide a ring-opening methases polymer hydrogenated having a molecular weight distribution, and also to provide a method for producing such a polymer hydrogenated.

MEANS TO SOLVE THE PROBLEM The present inventors examined various in order to solve the said problem, and used the ring-opening metathesis polymer hydrogenated substance of the cyclic olefin type monomer for the resist material which has the outstanding optical characteristic, electrical property, rigidity, heat resistance, substrate adhesiveness, and weather resistance. The possibility of use as a base polymer has been intensively studied. As a result, a new ring opening having a specific structural unit, that is, an aliphatic cyclic compound as a main chain and having a structural unit containing an oxygen atom in a part of the cyclic structure is disclosed. It has been found that the metathesis polymer hydrogenated substance satisfies various performances as these resist materials, and have completed the present invention.

That is, this invention is the following general formula [1]:

[Wherein, R ¹ ~R ^4, wherein at least one of the following general formula [2]:

(Wherein a chain line represents a bonding element. R ⁵ represents a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms, Or a straight, branched or cyclic acyl group having 1 to 10 carbon atoms R ⁶ represents a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms W ¹ represents a single bond or 1 carbon atom; Z represents a (k + 2) valent hydrocarbon group of 10. Z represents a divalent hydrocarbon group of 2 to 15 carbon atoms, and forms a monocyclic or temporary exchange with the carbon atoms to be bonded. 1) is a functional group having a tertiary ester group of cyclic alkyl, and each of R ¹ to R ⁴ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Halogen, C1-C20 straight chain, minute A cyclic or cyclic halogenated alkyl group, a straight or branched alkoxy group having 1 to 20 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a straight chain having 2 to 20 carbon atoms, Branched or cyclic alkylcarbonyloxy group, C6-C20 arylcarbonyloxy group, C1-C20 linear, branched or cyclic alkylsulfonyloxy group, C6-C20 arylsulfonyl jade Is selected from a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and X ¹ is -O- or- CR ⁷ _2- (R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms) and may be the same or different. j represents 0 or an integer of 1 to 3; and contains a structural unit [A] represented by

Furthermore, the following general formula [3]:

[Wherein, R ⁸ to R ¹¹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and X ² is -O- or -CR ¹² _2- (R ¹² is Hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and may be the same or different. m represents 0 or an integer of 1 to 3. Structural unit [B] and / or the following general formula [4]:

[Wherein, R ¹³ ~R ¹⁶ are, each independently, a hydrogen atom or a linear of 1 to 10 carbon atoms, an alkyl group of branch-like or ring-shaped, X ³ is -O- or -CR ¹⁷ ₂ - (R ¹⁷ is Hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and may be the same or different. One of Y ¹ and Y ² is-(C = O)-and the other is -CR ¹⁸ _2- (R ¹⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms) to be. n represents 0 or an integer of 1 to 3; and at least contains a structural unit [C] represented by

X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3] and of the structural unit [C] represented by the general formula [4] At least one of X ³ is -O-,

Ring opening whose molar ratio [A] / ([B] and [C]) is 0/100-99/1, and the ratio (Mw / Mn) of weight average molecular weight Mw and number average molecular weight Mn is 1.0-2.0 It provides a metathesis polymer hydrogenation.

Moreover, this invention is the following general formula [9]:

(Wherein R ¹ to R ⁴ , X ¹ and j are the same as defined above), a cyclic olefin monomer represented by the following general formula is used, if desired.

Wherein R ⁸ to R ¹¹ , X ² and m are the same as defined above, and the cyclic olefin monomer represented by the above formula and / or the following general formula [11]:

Using at least the annular olefin monomer represented by ^{(wherein, R 13 ~R 16, X 3} , Y 1, Y 2 and n are also same as defined above), and further by the general formula [9] X ^1, formula At least one of X ^{2 in} [10] and X ³ in Formula [11] is -O-,

A method for producing a ring-opening metathesis polymer hydrogenated product of the first aspect of the present invention is characterized by polymerizing these monomers with a ring-opening metathesis catalyst and further hydrogenating in the presence of a hydrogenation catalyst.

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated.

In the general formula [1] of the present invention, at least one of R ¹ to R ⁴ is the following general formula [2]:

(Wherein a chain line represents a bonding element. R ⁵ represents a hydrogen atom, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms, Or a straight, branched or cyclic acyl group having 1 to 10 carbon atoms R ⁶ represents a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms W ¹ represents a single bond or 1 carbon atom; Z represents a (k + 2) valent hydrocarbon group of 10. Z represents a divalent hydrocarbon group of 2 to 15 carbon atoms, and forms a monocyclic or temporary exchange with the carbon atoms to be bonded. K is 0 or 1. It is a functional group which has a tertiary ester group of cyclic alkyl represented by these.

In R ⁵ , examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl and cyclo Hexyl, 1-ethylcyclopentyl, 1-ethylcyclohexyl, etc. are mentioned, As a C2-C10 linear, branched or cyclic alkoxyalkyl group, For example, methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, etc. are mentioned. Examples of the linear, branched or cyclic acyl group having 1 to 10 carbon atoms include formyl, acetyl, pivaloyl and cyclohexylcarbonyl. Among these R ⁵ , a linear or branched alkyl group having 1 to 6 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 7 carbon atoms, and a straight or branched acyl group having 2 to 7 carbon atoms are preferable. In particular, hydrogen atoms, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.

In R ⁶ , examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl and cyclohexyl. , Cyclooctyl, norbornyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylnorbornyl, 1-ethylnorbornyl, and the like. Of these, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, norbornyl, 1-ethylcyclopentyl and 1-ethylcyclohexyl are preferable.

In W ^1, of 1 to 10 carbon atoms as the (k + 2) valent hydrocarbon group, and when k is 0, a carbon number of 1 to 10 linear, and a divalent hydrocarbon group of branch-like or annular, for example, methylene , Dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-cyclopentylene , 1,2-cyclopentylene, 1,3-cyclopentylene, 1,1-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclohexylene and 1,4-cyclohexylene Can be mentioned. Among these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene and 2-methyltrimethylene are preferable. In the case where k is 1, for example, one obtained by removing one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned above when k is 0 is used as a coupling element. Most preferred W ¹ is a single bond.

Z is a C2-C15 divalent hydrocarbon group and is a hydrocarbon group which forms monocyclic or cross-exchange with the carbon atom couple | bonded. For example, the following general formula [13]:

(Wherein a chain line represents a bonding element. R ⁶ is the same as defined above. R ³² to R ³⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. B Is an integer of 0 or 1 to 6, and when b is 2 to 6, a plurality of R ³⁴ and R ³⁵ may be the same as or different from each other.) A 1-alkylcycloalkyl group represented by the following general formula [14]:

(Wherein, the chain line represents a bonding element. R ⁶ is the same as defined above. R ³⁸ to R ⁴⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.) 2-alkyl-2-bornaneyl group and 2-alkyl- 2-adamantyl group, such as 2-methyl- 2-adamantyl and 2-ethyl- 2-adamantyl, are mentioned. As a specific example of General formula [13], 1-methylcyclopropyl, 1-methylcyclobutyl, 1-ethylcyclobutyl,

1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl,

1-iso-propylcyclopentyl, 1-tert-butylcyclopentyl, 1-cyclopentylcyclopentyl,

1-cyclohexylcyclopentyl, 1-norbornylcyclopentyl, 1-methylcyclohexyl,

1-ethylcyclohexyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylcycloheptyl,

1-ethylcycloheptyl, 1-methylcyclooctyl, 1-methylcyclononyl, and the like, among which 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl,

1-iso-propylcyclopentyl, 1-tert-butylcyclopentyl, 1-cyclopentylcyclopentyl,

[Chemical Formula 15], such as 1-cyclohexylcyclopentyl and 1-norbornylcyclopentyl:

1-alkylcyclopentyl represented by is preferred, more preferably 1-methylcyclopentyl [15-1] and 1-ethylcyclopentyl [15-2]. As a specific example of General formula [14], the following general formula [16]:

2-alkyl norbornyl groups, such as these, are mentioned, Among these, [16-1], [16-2], [16-3], and [16-4] are preferable.

The other groups in R ¹ to R ⁴ are each independently a hydrogen atom, a linear or branched chain such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 20 carbon atoms. Or halogen such as cyclic alkyl group, chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl of 1 to 20 carbon atoms, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, Linear, branched or cyclic halogenated alkyl groups such as trifluoromethyl, trichloromethyl or tribromomethyl, methoxy of 1 to 12 carbon atoms, ethoxy, isopropoxy, n-butoxy, tert-part Linear, branched or cyclic alkoxy groups such as oxy or menthoxy, methoxymethyl of 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol, or Contains alkoxysaccharides, such as methyl glucose Is an arylcarbo such as a linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkylcarbonyloxy group such as acetoxy having 2 to 20 carbon atoms, or naphthoyloxy having 6 to 20 carbon atoms. Linear, branched or cyclic alkylsulfonyloxy groups, such as a silyloxy group, mesyloxy having 1 to 20 carbon atoms, arylsulfonyloxy groups such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl having 2 to 20 carbon atoms, Linear, branched or cyclic alkoxy such as ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl or cyclohexyloxycarbonyl Carbonyl group, methoxycarbonylmethyl having 3 to 20 carbon atoms, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl, n Propoxycarbonylmethyl, isopropoxycarbonylmethyl As a specific example, linear, branched, or cyclic alkoxycarbonylalkyl groups, such as n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or cyclohexyloxycarbonylmethyl, are mentioned. Among these, hydrogen atoms, straight-chain, branched or cyclic alkyl groups having 1 to 20 carbon atoms, straight-chain or branched or cyclic alkoxy groups having 1 to 20 carbon atoms, straight-chain or branched carbon atoms having 2 to 20 carbon atoms; A cyclic alkoxyalkyl group, a C2-C20 linear, branched or cyclic alkoxycarbonyl group, and a C3-C20 linear, branched or cyclic alkoxycarbonylalkyl group are preferable, More preferably, hydrogen It is an atom, a C1-C10 linear or branched alkyl group, a C2-C10 linear or branched alkoxycarbonyl group, and a C3-C10 linear or branched alkoxycarbonylalkyl group.

X ¹ is —O— or —CR ⁷ ₂ — (R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when j is 1 to 3, X ¹ may be the same. You may differ. Examples of R ⁷ include a hydrogen atom or a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl having 1 to 10 carbon atoms. As X ¹ , it is preferably -O- or -CH _2- , more preferably all X ¹ are either -O- or -CH _2- . As j, Preferably it is 0 or 1.

That is, as a specific example of General formula [1], following General formula [17]:

Structural unit [A] shown by these etc. are mentioned.

In General Formula [3], R ⁸ to R ¹¹ are each independently a hydrogen atom or methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or cyclohexyl having 1 to 10 carbon atoms. Or a linear, branched or cyclic alkyl group such as menthyl. X ² is —O— or —CR ¹² ₂ — (R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when m is 1 to 3, X ² may be the same. You may differ. As R <^{12>, a} hydrogen atom or a linear or branched alkyl group, such as C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As X ² , it is preferably -O- or -CH _2- , more preferably all X ² are either -O- or -CH _2- . As m, Preferably, it is 0 or 1.

That is, as a specific example of General formula [3], following General formula [18]:

Structural unit [B] shown by these etc. are mentioned.

In General Formula [4], each of R ¹³ to R ¹⁶ is independently a hydrogen atom or methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclo or C1-C10. Examples of the linear, branched or cyclic alkyl group such as hexyl or menthyl can be given. X ³ is —O— or —CR ¹⁷ ₂ — (R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when n is 1 to 3, X ³ may be the same. You may differ. As R <^{17>, a} hydrogen atom or a linear or branched alkyl group, such as C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As X ³ , it is preferably -O- or -CH _2- , and more preferably all X ³ are either -O- or -CH _2- . One of Y ¹ and Y ² is-(C = O)-and the other is -CR ¹⁸ _2- (R ¹⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms) to be. As R <^{18>, a} hydrogen atom or a linear or branched alkyl group, such as a C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As Y ¹ and Y ² , one side is preferably-(C = O)-and the other is -CH _2- . As n, Preferably, it is 0 or 1.

That is, as a specific example of General formula [4], following General formula [19]:

Structural unit [C] represented by these etc. are mentioned.

The ring-opening metathesis polymer hydrogenated substance in this invention is X < ¹ > of structural unit [A] represented by general formula [1], X < ² > of structural unit [B] represented by general formula [3], and general formula At least one of X ³ of the structural unit [C] represented by [4] is -O-, a ring-opening metathesis polymer hydrogenated substance, and the oxygen atom is present in the aliphatic cyclic compound having a main chain, whereby It has the effect of further improving the solubility in polar organic solvents, such as ketones and alcohols, used in the process of applying to the silicon wafer of a resist, the adhesiveness to a process board, the improvement of the wetting tension at the time of image development by alkaline aqueous solution, and The affinity with respect to water is also improved, and the developability with respect to release agents (or developer), such as alkaline aqueous solution after exposure, also improves. Preferably, X ¹ of structural unit [A] represented by General Formula [1], X ² of structural unit [B] represented by General Formula [3] and structural unit [C] represented by General Formula [4] And at least one of X ³ in] is —O— and the other is —CH ₂ —. The molar amount of -O-units with respect to the total molar amount of X ¹ , X ² and X ³ is 0.01 to 0.99, preferably 0.02 to 0.95, more preferably 0.05 to 0.80, most preferably 0.10 to 0.70.

In the present invention, the molar ratio of the structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [3] and / or the structural unit [C] represented by the general formula [4] [A] / ([B] and [C]) is 0/100-99/1, Preferably it is 20/80-99/1. It is essential that at least a certain amount of structural units [B] and / or [C] are present. Here, the structural unit [A] contains a tertiary ester group of cyclic alkyl represented by the general formula [2], that is, a group which is decomposed by an acid generated from a photosensitive agent at the time of exposure to produce carboxylic acid, and after exposure It is necessary to develop a resist pattern by developing with alkaline aqueous solution. In addition, the structural units [B] and / or [C] are necessary for expressing the adhesiveness with the substrate to be processed, such as a silicon substrate. If these molar ratios [A] / ([B] and [C]) are less than 20/80, development may become inadequate. Moreover, when it exceeds 99/1, adhesiveness with a to-be-processed substrate will not be expressed. More preferably, the molar ratios [A] / ([B] and [C]) are 20/80 to 95/5, particularly preferably 25/75 to 90/10, and most preferably 30/70 to 85 / 15. These structural units are in this range, which are suitable for preparing a resist composition, are dissolved in a polar solvent such as 2-heptanone together with a highly polar photosensitive agent, and are used on a substrate such as a silicon substrate. It is extremely important as a resist material to apply | coat. That is, when the ring-opening metathesis polymer hydrogenated agent prepares the resist composition, it is possible to form a uniform smooth coating film by increasing the solubility or dissolution rate in the polar solvent.

In the ring-opening metathesis polymer hydrogenated product of the present invention, at least one of the structural unit [B] or [C] is essential, and is added to the structural unit [A] to form a structural unit [B] and [C]. Although it may be a copolymer, it is preferably a binary polymer composed of only one of structural units [B] or [C].

In the ring-opening metathesis polymer hydrogenated product of the present invention, the ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn is limited to a narrow molecular weight distribution of 1.0 to 2.0. The molecular weight distribution greatly affects the resolution when used as a resist material, and the narrower the pattern, the higher the resolution. Preferably it is 1.0-1.8, More preferably, it is the range of 1.0-1.6. The molecular weight of the ring-opening metathesis polymer hydrogenated product of this invention is 500-200,000 normally, and number average molecular weight Mn is preferably 1,000-100,000, More preferably, it is 3,000-50,000. In addition, the number average molecular weight and the weight average molecular weight described in this specification were measured by the gel permeation chromatography (GPC) in polystyrene conversion.

Moreover, these ring-opening metathesis polymer hydrogenated products may consist of one type of structural unit, respectively, of structural unit [A], [B], and / or [C], but any one or all of each structural unit It may consist of two or more types of structural units. For example, structural unit [A] has the following general formula [1-1] and [1-2]:

(In formula, at least 1 of R <^48> -R <^51> is a functional group which has a tertiary ester group of cyclic alkyl represented by General formula [2], and other R <^48> -R <^51> is respectively independently a hydrogen atom and C1-C1 A linear, branched or cyclic alkyl group of -20, a halogen, a linear, branched or cyclic halogenated alkyl group of 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group of 1 to 20 carbon atoms, C2-C20 linear, branched or cyclic alkoxyalkyl group, C2-C20 linear, branched or cyclic alkylcarbonyloxy group, C6-C20 arylcarbonyloxy group, C1 A linear, branched or cyclic alkylsulfonyloxy group of -20, an arylsulfonyloxy group of 6 to 20 carbon atoms, a straight, branched or cyclic alkoxycarbonyl group of 2 to 20 carbon atoms, or a straight chain of 3 to 20 carbon atoms shape, Shape selected from the group or alkoxycarbonylalkyl group, and a ring-shaped, and j ¹ represents 0 or an integer of 1 to 3).

(Wherein, at least one of R ⁵² to R ⁵⁵ is a functional group having a tertiary ester group of cyclic alkyl represented by the general formula [2], and other R ⁵² to R ⁵⁵ are each independently a hydrogen atom or carbon number 1). A linear, branched or cyclic alkyl group of -20, a halogen, a linear, branched or cyclic halogenated alkyl group of 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group of 1 to 20 carbon atoms, C2-C20 linear, branched or cyclic alkoxyalkyl group, C2-C20 linear, branched or cyclic alkylcarbonyloxy group, C6-C20 arylcarbonyloxy group, C1 A linear, branched or cyclic alkylsulfonyloxy group having from 20 to 20 carbon atoms, an arylsulfonyloxy group having from 6 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having from 2 to 20 carbon atoms, or having 3 to 20 carbon atoms Straight Line, And a structural unit [A-1] and [A-2] selected from a branched or cyclic alkoxycarbonylalkyl group, j ² represents an integer of 0 or 1-3. B] is the following general formula [3-1] and [3-2]:

(In formula, R <^56> -R <^59> is respectively independently a hydrogen atom or a C1-C10 linear, branched or cyclic alkyl group, and m <^1> represents the integer of 0 or 1-3.)

(In formula, R <^60> -R <^63> is respectively independently a hydrogen atom or a C1-C10 linear, branched, or cyclic alkyl group, and m <^2> represents the integer of 0 or 1-3.) The structural units [B-1] and [B-2] and / or structural units [C] to be represented are the following general formulas [4-1] and [4-2]:

(In formula, R <^64> -R <^67> is respectively independently a hydrogen atom or a C1-C10 linear, branched, or cyclic alkyl group, and Y <^3> and Y <^4> are each-(C = O)-. The other is -CH _2- , and n ¹ represents 0 or an integer of 1 to 3.)

(Wherein R ⁶⁸ to R ⁷¹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and Y ⁵ and Y ^{6 each} represent-(C = O)-; The other is -CH _2- , and n ² represents 0 or an integer of 1 to 3). The ring-opened metathesis polymer hydrogenated product of structural units [C-1] and [C-2] represented by Can be mentioned.

The ring-opening metathesis copolymer hydrogenated substance of the present invention is, in addition to the structural units [A] and [B] and / or [C], a structural unit [D] represented by the general formula [5] as a structural unit. It is preferable to have it, since the board | substrate adhesiveness and affinity to a developing solution further improve.

In general formula [5] of the present invention, at least one of R ¹⁹ to R ²² is represented by general formula [6] (wherein, the chain line represents a bonding element. R ²³ represents a hydrogen atom and a straight chain having 1 to 10 carbon atoms. , represents a branched shape or a ring-shaped alkyl group, having 2 to 10 carbon atoms of linear, branched form or cyclic alkoxyalkyl group, or a C1-10 linear, branched form or cyclic acyl. W ² is a single A bond or a hydrocarbon group having a (k + 2) valence of 1 to 10 carbon atoms is represented, q is 0 or 1).

In R ²³ , as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl And 1-ethylcyclopentyl, 1-ethylcyclohexyl, and the like. Examples of the C2-C10 straight, branched or cyclic alkoxyalkyl group include, for example, methoxymethyl, 1-ethoxyethyl, 1 -tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like. As a C1-C10 linear, branched, or cyclic acyl group, formyl, acetyl, pivaloyl, cyclohexylcarbonyl, etc. are mentioned, for example. Among these R ²³ , a linear or branched alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 7 carbon atoms, and a straight or branched acyl group having 2 to 7 carbon atoms are preferable. In particular, hydrogen atoms, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.

In the W ^2, as the (q + 2) valent hydrocarbon group having 1 to 10 carbon atoms, q is 0, carbon atoms, linear, branched shape or a divalent cyclic hydrocarbon group of 1 to 10, for example, methylene , Dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-cyclopentylene , 1,2-cyclopentylene, 1,3-cyclopentylene, 1,1-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclohexylene and 1,4-cyclohexylene Can be mentioned. Among these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene and 2-methyltrimethylene are preferable. In the case where k is 1, for example, one obtained by removing one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned above when k is 0 is used as a coupling element. Most preferred W ² is a single bond.

The others in R ¹⁹ to R ²² are each independently a hydrogen atom, a linear, branched form such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl, or Halogen such as cyclic alkyl group, chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl of 1 to 20 carbon atoms, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, tri Linear, branched or cyclic halogenated alkyl groups such as fluoromethyl, trichloromethyl or tribromomethyl, methoxy of 1 to 12 carbon atoms, ethoxy, isopropoxy, n-butoxy and tert-butoxy Or methyl, such as a linear, branched or cyclic alkoxy group such as menthoxy, methoxymethyl having 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol or Containing alkoxysaccharides such as glucose Arylcarbonyl jades such as linear, branched or cyclic alkoxyalkyl groups, linear or branched alkylcarbonyloxy groups such as acetoxy having 2 to 20 carbon atoms, and naphthoyloxy having 6 to 20 carbon atoms Alkylsulfonyloxy groups, such as a C1-C20 mesyloxy, Aryl sulfonyloxy groups, such as a C6-C20 tosyloxy, C2-C20 methoxycarbonyl, ethoxycarbonyl, n-propoxycar Linear, branched or cyclic alkoxycarbonyl groups, such as carbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl or cyclohexyloxycarbonyl, methoxycarbons having 3 to 20 carbon atoms Carbonylmethyl, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxy Carbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycar Linear, such as carbonyl-methyl or cyclohexyloxy carbonyl methyl Brassica Viterbo, there may be mentioned an alkoxycarbonyl group of branch-like or annular shape as a specific example. Among these, hydrogen atoms, straight-chain, branched or cyclic alkyl groups having 1 to 20 carbon atoms, straight-chain or branched or cyclic alkoxy groups having 1 to 20 carbon atoms, straight-chain or branched carbon atoms having 2 to 20 carbon atoms; A cyclic alkoxyalkyl group, a C2-C20 linear, branched or cyclic alkoxycarbonyl group, and a C3-C20 linear, branched or cyclic alkoxycarbonylalkyl group are preferable, More preferably, hydrogen It is an atom, a C1-C10 linear or branched alkyl group, a C2-C10 linear or branched alkoxycarbonyl group, and a C3-C10 linear or branched alkoxycarbonylalkyl group.

X ⁴ is —O— or —CR ²³ ₂ — (wherein R ²³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when p is 1 to 3, X ⁴ is It may be same or different. As R <^23> , a hydrogen atom or a linear or branched alkyl group, such as C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As X ⁴ , it is preferably -O- or -CH _2- , more preferably all X ⁴ are either -O- or -CH _2- . As p, Preferably it is 0 or 1.

That is, as a specific example of General formula [5], following General formula [20]:

Structural unit [D] shown by etc. are mentioned.

In a preferred embodiment of the present invention, the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3] and the structural unit [4] represented by the general formula [4] The molar ratio ([A] + [B] + [C]) / [D] of the structural unit [D] represented by the general formula [5] to C] is 100/0 to 20/80, and the structural unit [A In addition to], [B], and [C], it is preferable that some fixed amount of structural unit [D] exists. Here, the structural unit [D] extremely improves the adhesion to the substrate to be processed such as the silicon substrate and improves the affinity with the developer. Preferably, the molar ratio ([A] + [B] + [C]) / [D] is 98/2 to 50/50, more preferably 97/3 to 60/40, most preferably 95 / 5 to 70/30.

The ring-opened metathesis copolymer hydrogenated substance of the present invention is a structural unit represented by the general formula [7] in addition to the structural units [A] and [B] and / or [C], preferably [D]. You may also have [E] as a structural unit.

In General Formula [7], at least one of R ²⁴ to R ²⁷ is represented by General Formula [8] (wherein the chain line represents a bonding element. R ²⁸ represents a hydrogen atom, a straight chain having 1 to 10 carbon atoms, and a branched shape. or an alkyl group of cyclic, having 2 to 10 carbon atoms represents a linear, branched form or cyclic alkoxyalkyl group, or a linear group of 1 to 10 carbon atoms, or an acyl group branch shape of the ring-shaped. R ²⁹ is 1 to 10 carbon atoms a linear or branched alkyl group shape, and displays a linear, branch-like, or an alkoxyalkyl group, linear, branched shape or a halogenated alkyl group of 1 to 20 carbon atoms in the annular ring-shaped with a carbon number of 2~10. W ³ is a single A bond or a hydrocarbon group having a (k + 2) valence of 1 to 10 carbon atoms is indicated, s is 0 or 1.) and a functional group having a carboxylic acid ester group represented by.

In R ²⁸ , examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl and cyclohexyl. And 1-ethylcyclopentyl, 1-ethylcyclohexyl, and the like. Examples of the C2-C10 straight, branched or cyclic alkoxyalkyl group include, for example, methoxymethyl, 1-ethoxyethyl, 1 -tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like. As a C1-C10 linear, branched, or cyclic acyl group, formyl, acetyl, pivaloyl, cyclohexylcarbonyl, etc. are mentioned, for example. Among these R ²⁸ , a linear or branched alkyl group having 1 to 6 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 7 carbon atoms, and a straight or branched acyl group having 2 to 7 carbon atoms are preferable. In particular, hydrogen atoms, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are preferred.

In R ²⁹ , examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. As a linear, branched or cyclic alkoxyalkyl group of -10, for example, methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl, etc. are mentioned, As a C1-C20 linear, branched or cyclic halogenated alkyl group, it is an example. Examples thereof include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl and the like. Among these R ²⁹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl are particularly preferable.

In W ³ , as the (s + 2) -valent hydrocarbon group having 1 to 10 carbon atoms, when s is 0, it is a straight-chain, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms, for example, methylene. Dimethylmethylene, ethylidene, propylidene, butylidene, ethylene,

1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene, 1-ethyl-2-methylethylene, Trimethylene,

1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene,

Pentamethylene, 1,1-cyclopentylene, 1,2-cyclopentylene, 1,3-cyclopentylene,

1,1-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, etc. are mentioned. Among these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene and 2-methyltrimethylene are preferable. In the case where s is 1, for example, one obtained by removing one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned above when s is 0 is used as a coupling element. Most preferred W ³ is a single bond.

The other of R ²⁴ to R ²⁷ is each independently a hydrogen atom, linear, branched form such as methyl having 1 to 20 carbon atoms, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl or Halogen such as cyclic alkyl group, chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl of 1 to 20 carbon atoms, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, tri Linear, branched or cyclic halogenated alkyl groups such as fluoromethyl, trichloromethyl or tribromomethyl, methoxy of 1 to 12 carbon atoms, ethoxy, isopropoxy, n-butoxy and tert-butoxy Or methyl, such as a linear, branched or cyclic alkoxy group such as menthoxy, methoxymethyl having 2 to 20 carbon atoms, methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol or Containing alkoxysaccharides such as glucose Arylcarbonyl jades such as linear, branched or cyclic alkoxyalkyl groups, linear or branched alkylcarbonyloxy groups such as acetoxy having 2 to 20 carbon atoms, and naphthoyloxy having 6 to 20 carbon atoms Linear, branched or cyclic alkylsulfonyloxy groups such as mesyloxy having 1 to 20 carbon atoms, arylsulfonyloxy groups such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl having 2 to 20 carbon atoms, and Linear, branched or cyclic alkoxy such as oxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, or cyclohexyloxycarbonyl Carbonyl group, methoxycarbonylmethyl having 3 to 20 carbon atoms, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- (ethoxycarbonyl) ethyl, n Propoxycarbonylmethyl, isopropoxycarbonylmethyl, n- As a specific example, linear, branched, or cyclic alkoxycarbonylalkyl groups, such as butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or cyclohexyloxycarbonylmethyl, are mentioned. Among these, hydrogen atoms, straight-chain, branched or cyclic alkyl groups having 1 to 20 carbon atoms, straight-chain or branched or cyclic alkoxy groups having 1 to 20 carbon atoms, straight-chain or branched carbon atoms having 2 to 20 carbon atoms; A cyclic alkoxyalkyl group, a C2-C20 linear, branched or cyclic alkoxycarbonyl group, and a C3-C20 linear, branched or cyclic alkoxycarbonylalkyl group are preferable, More preferably, hydrogen It is an atom, a C1-C10 linear or branched alkyl group, a C2-C10 linear or branched alkoxycarbonyl group, and a C3-C10 linear or branched alkoxycarbonylalkyl group.

X ⁵ is —O— or —CR ³⁰ ₂ — (R ³⁰ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.) When r is 1 to 3, X ⁵ may be the same. You may differ. As R <^30> , a hydrogen atom or a linear or branched alkyl group, such as C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, is mentioned as a specific example. As X ⁵ , it is preferably -O- or -CH _2- , more preferably all X ⁵ are either -O- or -CH _2- . As r, it is preferably 0 or 1.

That is, as a specific example of General formula [7], following General formula [21]:

Structural unit [E] shown by etc. are mentioned.

The ring-opening metathesis copolymer hydrogenated substance of the present invention is added to structural units [A] and [B] and / or [C], preferably to [D], and optionally [E] In addition to]

The following general formula [22]:

[Wherein, R ⁷² to R ⁷⁵ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a halogen, a linear, branched or cyclic halogenated group having 1 to 20 carbon atoms; Alkyl group, C1-C20 linear, branched or cyclic alkoxy group, C2-C20 linear, branched or cyclic alkoxyalkyl group, a hydroxyl group, C2-C20 linear, branched form Or a cyclic hydroxyalkyl group, cyano group, straight-chain, branched or cyclic cyanoalkyl group having 2 to 20 carbon atoms, straight-chain, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, and carbon atoms C3-C20 linear, branched or cyclic alkylcarbonyloxyalkyl group, C6-C20 arylcarbonyloxy group, C1-C20 linear, branched or cyclic alkylsulfonyloxy group, carbon Is selected from a linear, branched or cyclic alkylsulfonyloxyalkyl group having 2 to 20 carbon atoms, or an arylsulfonyloxy group having 6 to 20 carbon atoms, and X ⁶ is -O- or -CR ⁷⁶ _2- (R ⁷⁶ is Hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and may be the same or different. v represents O or an integer of 1 to 3; and may have, as a structural unit, a structural unit [F].

The ring-opening metathesis copolymer hydrogenated product of the present invention is represented by the structural unit [A] represented by the general formula [1], the structural unit [B] and / or the general formula [4] represented by the general formula [3]. Cyclic olefin monomers corresponding to each of the structural unit [C] and structural unit [E] represented by the general formula [7] as necessary, and structural unit [F] represented by the general formula [22] as necessary. Is obtained by polymerization of a ring-opening metathesis catalyst and hydrogenation under a hydrogenation catalyst.

The cyclic olefin monomer corresponding to the structural unit [A] represented by the general formula [1] is a cyclic olefin monomer having the structure of the general formula [9], and the structural unit [B] represented by the general formula [3] The cyclic olefin monomer corresponding to the above is a cyclic olefin monomer having a structure of the general formula [10], and the cyclic olefin monomer corresponding to the structural unit [C] represented by the general formula [4] is a general formula [11] Is a cyclic olefin monomer having a structure of], and the cyclic olefin monomer corresponding to the structural unit [E] represented by the general formula [7] is a cyclic olefin monomer having the structure of Formula [12], The cyclic olefin monomer corresponding to the structural unit [F] represented by [22] is the following general formula [23]:

(Wherein R ⁷² to R ⁷⁵ , X ⁶ and v are the same as defined above).

In addition, as a specific example of R <^56> -R <^75> in these formula, it is the substituent already described as a corresponding substituent, respectively, and the same substituent including a preferable range is mentioned.

That is, the ring-opening metathesis copolymer hydrogenated product of the present invention is at least a cyclic olefin monomer represented by the general formula [9], a cyclic olefin monomer represented by the general formula [10] and / or a general formula [11]. A cyclic olefin monomer represented by &lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt; Further, if necessary by the general formula [9] in the X ^1, general formula [10] X ^2, and general formula [11] of the at least one of X ³ is -O- of these cyclic olefin monomers, ring-opening metathesis catalyst It is obtained by superposing | polymerizing with and hydrogenating under a hydrogenation catalyst. Preferably, the injection molar ratio of the cyclic olefin monomer represented by the general formula [9], the cyclic olefin monomer represented by the general formula [10] and the cyclic olefin monomer represented by the general formula [11] is 1 / 100-99 / 1, preferably 20 / 80-99 / 1, more preferably 20 / 80-95 / 5, particularly preferably 25 / 75-90 / 1, most preferably 30 / 70- 85/15. When using the cyclic olefin monomer represented by General formula [12], the amount of 50 mol% or less is generally used with respect to the total molar amount of the olefin monomer to be used, Preferably it is 30 mol% or less, More preferably, Is less than 20%. In addition, when using the cyclic olefin monomer represented by General formula [23], it is normally used in the amount of 50 mol% or less with respect to the total molar amount of the olefin monomer to be used, Preferably it is 30 mol% or less, Furthermore, Preferably it is 20 mol% or less.

At least ^one of X ¹ of the cyclic olefin monomer represented by the general formula [9], X ² of the cyclic olefin monomer represented by the general formula [10] and X ³ of the olefin monomer represented by the general formula [11]. Is -O-, and others are -CH _2- , and the molar amount of -O-units relative to the total molar amount of X ¹ , X ² and X ³ is 0.01 to 0.99, preferably 0.02 to 0.95 More preferably, it is 0.05-0.80, Most preferably, it is 0.10-0.70. Moreover, also when using the cyclic olefin monomer represented by general formula [12] and / or general formula [23], with respect to the sum total unit mole amount of X <^1> , X <^2> , X <^3> , X <^5> and X <^6> . The molar amount of the O-unit is 0.01 to 0.99, preferably 0.02 to 0.95, more preferably 0.05 to 0.80, and most preferably 0.10 to 0.70.

The ring-opening metathesis copolymer hydrogenated product of the present invention is a ring-opening metathesis catalyst, preferably a living ring-opening metathesis catalyst, using the cyclic olefin monomer, more preferably a chain such as olefin or dimen. (Iii) It is obtained by superposing | polymerizing in a solvent or a solvent-free in presence of a transfer agent, and then hydrogenating in a solvent using the hydrogenation catalyst under hydrogen pressure.

The polymerization catalyst used in the present invention may be any catalyst as long as it is a catalyst for ring-opening metathesis polymerization.

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHBu ^t ) ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ ,

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHBu ^t ) (OCMe ₂ (CF ₃ ) ₂ ) ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OBu ^t ) ₂ ,

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OCMe ₂ CF ₃ ) ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) Tungsten-based alkylidene catalysts such as (OCMe ₂ (CF ₃ ) ₂ ) ₂ (where Pr ⁱ represents an iso-propyl group, Bu ^t represents a tert-butyl group, Me represents a methyl group and Ph represents a phenyl group); W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OBu ^t ) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OBu ^t ) ₂ (PMe ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OBu ^t ) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) ₂ (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) ₂ (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (PMe ₃ ),

W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (PMe ₃ ),

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCHCMePh) (OCMe (CF ₃ ) ₂ ) ₂ (PMe ₃ ),

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCHCMePh) (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ),

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCHCMePh) (OPh) ₂ (PMe ₃ ) (where Pr ⁱ is an iso-propyl group, Bu ^t is a tert-butyl group, Me is a methyl group, Ph represents a phenyl group) tungsten-based alkylidene catalysts;

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHBu ^t ) (OBu ^t ) ₂ , Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ ,

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHBu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ , Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph ) (OBu ^t ) ₂ ,

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OCMe ₂ CF ₃ ) ₂ ,

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ (where Pr ⁱ is an iso-propyl group, Bu ^t is a tert-butyl group, Me Molybdenum-based alkylidene catalysts such as a methyl group and Ph represents a phenyl group;

Re (CBu ^t ) (CHBu ^t ) (O-2,6-Pr ⁱ ₂ C ₆ H ₃ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (O-2-Bu ^t C ₆ H ₄ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (OCMe ₂ CF ₃ ) ₂ , Re (CBu ^t ) (CHBu ^t ) (OCMe (CF ₃ ) ₂ ) ₂ ,

Rhenium-based alkylidene catalysts such as Re (CBu ^t ) (CHBu ^t ) (O-2,6-Me ₂ C ₆ H ₃ ) ₂ (wherein Bu ^t represents a butyl group);

Ta [C (Me) C (Me) CHMe ₃ ] (O-2,6-Pr ⁱ ₂ C ₆ H ₃ ) ₃ Py, Ta [C (Ph) C (Ph) CHMe ₃ ] (O-2,6 Tantalum alkylidene catalysts such as -Pr ⁱ ₂ C ₆ H ₃ ) ₃ Py (wherein Me represents a methyl group, Ph represents a phenyl group, and Py represents a pyridine group);

Ruthenium-based alkylidene catalysts such as Ru (CHCHCPh ₂ ) (PPh ₃ ) ₂ Cl ₂ and Ru (CHCHCPh ₂ ) (P (C ₆ H ₁₁ ) ₃ ) ₂ Cl ₂ (wherein Ph represents a phenyl group); Tanacyclobutane catalyst is mentioned. The ring-opening metathesis catalyst may be used alone or in combination of two or more thereof.

In addition to the above catalyst, a living ring-opening metathesis catalyst system based on a combination of an organic transition metal complex and Lewis acid as a promoter, for example, an organic aluminum compound and an organic tin as a transition metal halogen complex such as molybdenum and tungsten and a promoter A ring-opening metathesis catalyst composed of a compound or an organometallic compound such as lithium, sodium, magnesium, zinc, cadmium or boron may be used.

As a specific example of the organic transition metal halogen complex,

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OBu ^t ) Cl ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OCMe ₂ CF ₃ ) Cl ₂ ,

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OCMe (CF ₃ ) ₂ ) Cl ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) ( OBu ^t ) Cl ₂ ,

W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OCMe ₂ CF ₃ ) Cl ₂ , W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (tHf) (OCMe ₂ Tungsten halogen complexes such as (CF ₃ ) ₂ ) Cl ₂ (wherein Pr ⁱ is an iso-propyl group, Bu ^t is a tert-butyl group, Me is a methyl group, Ph is a phenyl group, and thf is a tetrahydrofuran) And a catalyst consisting of a combination of the following organometallic compounds, or

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OBu ^t ) Cl ₂ , Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OCMe ₂ CF ₃ ) Cl ₂ ,

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OCMe (CF ₃ ) ₂ ) Cl ₂ , Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) ( OBu ^t ) Cl ₂ ,

Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (thf) (OCMe ₂ CF ₃ ) Cl ₂ , Mo (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (tHf) (OCMe ( CF ₃ ) ₂ ) Cl ₂ (where Pr ⁱ is iso-propyl group, Bu ^t is tert-butyl group, Me is methyl group, Ph is phenyl group, and thf is tetrahydrofuran) The catalyst which consists of a combination of the following organometallic compounds is mentioned.

Moreover, as a specific example of the organometallic compound as a promoter, trimethyl aluminum,

Triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride,

Di-n-butylaluminum, diethylaluminum monobromide,

Diethylaluminum monoiodide, diethylaluminum monohydride,

Organoaluminum compounds such as ethyl aluminum sesquichloride and ethyl aluminum dichloride,

Tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin,

Tetrabutyltin, tetraoctyltin, trioctyltin fluoride,

Trioctyl tin chloride, trioctyl tin bromide,

Trioctyl tin iodide, dibutyltin difluoride, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, butyl Organic tin compounds such as tin triiodide,

organic lithium compounds such as n-butyllithium, organic sodium compounds such as n-pentyl sodium,

Methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide,

organic magnesium compounds such as n-propyl magnesium bromide, t-butylmagnesium chloride and allyl magnesium chloride, organic zinc compounds such as diethyl zinc, organic cadmium compounds such as diethyl cadmium, tromethyl boron, triethyl boron and tri- Organic boron compounds, such as n-butyl boron, etc. are mentioned.

In the living ring-opening metathesis polymerization of the present invention, the molar ratio of the cyclic olefin-based monomer and the ring-opening metathesis catalyst is a transition metal alkylidene catalyst such as tungsten, molybdenum, rhenium, tantalum or ruthenium or titanacyclobutane catalyst. Is 2-10000 in molar ratio with respect to a cyclic olefin type monomer transition metal alkylidene complex, Preferably it is 10-5000. In the case of the ring-opening metasis catalyst composed of the organic transition metal halogen complex and the organometallic compound, the cyclic olefin monomer is 2 to 10000, preferably 10 to 5000, in molar ratio relative to the organic transition metal halogen complex. The organometallic compound is in the range of 0.1 to 10, preferably 1 to 5, in molar ratio with respect to the organic transition metal halogen complex.

In addition, in this invention, when superposing | polymerizing using a ring-opening metathesis catalyst, in order to improve a catalyst efficiency, it is preferable to superpose | polymerize in presence of chain transfer agents, such as an olefin or diene. Examples of the olefins used as the chain transfer agent include α-olefins such as ethylene, propylene, butene, pentene, hexene and octene, and further include vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane and allyltri. And silicon-containing olecins such as isopropylsilane. Non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, and 1,6-heptadiene can be given as dienes. Moreover, these olefins or dienes may be used individually or in combination of 2 or more types, respectively.

In the present invention, the amount of the olefin or diene to coexist is 0.001 to 1000 moles, preferably 0.01 to 100 moles with respect to the cyclic olefin monomer. The olefin or diene is in the range of 0.1 to 1000 equivalents, preferably 1 to 500 equivalents, relative to 1 equivalent of the alkylidene of the transition metal alkylidene complex.

In addition, the ring-opening metathesis polymerization of the present invention may be carried out using a solvent or without a solvent. As a solvent to be used, ethers such as tetrihydrofuran, diethyl ether, dibutyl ether, dimethoxyethane or dioxane Ryu,

Aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene,

Aliphatic hydrocarbons such as pentane, hexane or heptane, aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or decalin, or

Halogenated hydrocarbons, such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, or trichlorobenzene, etc. are mentioned, You may mix and use these 2 or more types.

Although the concentration of the ring-opening metathesis polymerization in the present invention is not the same or different depending on the reactivity of the cyclic olefin monomer and the solubility in the polymerization solvent, the concentration of the cyclic olefin monomer to the solvent is usually 0.001 to 500 mol / L, Preferably it is 0.01-100 mol / L, More preferably, it is the range of 0.05-50 mol / L. The reaction temperature also varies depending on the type and amount of the cyclic olefin monomer and ring-opening metathesis catalyst to be used, but is usually at a reaction temperature of -30 to 150 ° C, preferably 0 to 120 ° C, more preferably 15 to Temperature of 100 ° C. The reaction time is usually 1 minute to 10 hours, preferably 5 minutes to 8 hours, and more preferably 10 minutes to 6 hours.

After the polymerization reaction, the reaction is stopped with a deactivator such as aldehydes such as butyl aldehyde, ketones such as acetone, and alcohols such as methanol, and the ring-opened metathesis polymer solution can be obtained.

In the present invention, since the ring-opening metathesis polymerization is a living polymerization reaction of the polymer obtained by living ring-opening metathesis polymerization, a polymer having a desired molecular weight can be obtained by controlling the molar ratio of the monomer and the catalyst. In addition, a polymer having a desired molecular weight can be obtained by controlling the molar ratio of the monomer, the chain transfer agent and the catalyst while maintaining the living polymerization reaction by carrying out the living ring-opening metathesis polymerization in the presence of olefin or diene as the chain transfer agent. The molecular weight obtained by this living polymerization has the number average molecular weight Mn in polystyrene conversion of 500-200,000, Preferably it is 1,000-100,000, Especially preferably, it is 3,000-50,000. In addition, although there are some differences depending on the properties of the monomer and the chain transfer agent, the ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn is controlled in a narrow molecular weight distribution range of 1.0 to 2.0. The range of this molecular weight distribution does not change even after the cis polymer is hydrogenated in the presence of a hydrogenation catalyst. Preferably it is 1.0-1.8, More preferably, it is the range of 1.0-1.6. The molecular weight and narrow molecular weight distribution in this range are extremely important in forming a uniform smooth coating film in the process of dissolving the resist material in a solvent and applying it to a silicon wafer with a rotary spreader. Therefore, the living polymerization of the polymerization that determines the molecular weight and molecular weight distribution as the resist material reflects the function of the resist material which has enhanced solubility in polar solvents, adhesion or adhesion to the surface of a silicon wafer, and applicability to the surface thereof. It is extremely important in doing so.

As mentioned above, the ring-opening metathesis polymer which has an olefinic unsaturated bond in a principal chain part is obtained by superposing | polymerizing the cyclic olefin monomer of this invention with a ring-opening metathesis catalyst. In the present invention, the main chain portion of the ring-opening metathesis polymer in order to lower the area of the maximum absorption wavelength of the ultraviolet ray (UV), particularly in order to maximize the UV transmittance in this region with respect to the ArF excimer laser region having a wavelength of 193 nm. It is necessary to hydrogenate olefin of. In addition, a well-known hydrogenation catalyst can be used for this hydrogenation reaction.

As a specific example of the hydrogenation catalyst, as a heterogeneous catalyst, a supported metal catalyst in which metals such as palladium, platinum, nickel, rhodium and ruthenium are supported on a carrier such as carbon, silica, alumina, titania, magnesia, diatomaceous earth, synthetic zeolite, Or as a homogeneous catalyst,

Nickel naphthenate / triethylaluminum,

Nickel acetylacetonate / triisobutylaluminum,

Cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum chloride,

Rhodium acetate, dichlorobis (triphenylphosphine) palladium,

Chlorotris (triphenylphosphine) rhodium,

Dihydride tetrakis (triphenylphosphine) ruthenium and the like, and the following general formula [24] in the presence of hydrogen as a homogeneous catalyst:

MHwQxTyUz... … … [24]

Wherein M represents ruthenium, rhodium, osmium, iridium, palladium, platinum or nickel, H represents a hydrogen atom, Q represents a halogen atom, T represents CO, NO, toluene, acetonitrile or tetra Hydrofuran, U represents PR ′ ¹ R ′ ² R ′ ³ (P represents phosphorus, R ′ ¹ R ′ ² R ′ ³ represents the same or different linear, branched or cyclic alkyl, alkenyl, respectively , Aryl, alkoxy or allyloxy), w is an integer of 0 or 1, x is an integer of 1 to 3, y is an integer of 0 or 1, z is 2 to 4 It is also possible to hydrogenate using a hydrogenation catalyst composed of an organometallic complex and an amine compound represented by ().

Q in General formula [24] represents a halogen atom and can illustrate a chlorine, a fluorine, a bromine, or an iodine atom as a specific example. In addition, T represents CO, NO, toluene, acetonitrile or tetrahydrofuran, U represents an organophosphorus compound, and as an example, trimethylphosphine, triethylphosphine, triisopropylphosphine,

Tri-n-propylphosphine, tri-t-butylphosphine, tri-n-butylphosphine,

Tricyclohexylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, triphenylphosphine, methyldiphenylphosphine, tri-p-tolylphosphine, diethylphenylphosphine, dichloro (ethyl Phosphine, dichloro (phenyl) phosphine, chlorodiphenylphosphine, trimethylphosphite,

Triisopropyl phosphite and triphenyl phosphite can be illustrated.

As a specific example of the organometallic complex represented by general formula [24],

Dichlorobis (triphenylphosphine) nickel, dichlorobis (triphenylphosphine) palladium,

Dichlorobis (triphenylphosphine) platinum, chlorotris (triphenylphosphine) rhodium,

Dichlorotris (triphenylphosphine) osmium,

Dichlorohydride bis (triphenylphosphine) iridium,

Dichlorotris (triphenylphosphine) ruthenium,

Dichlorotetrakis (triphenylphosphine) ruthenium,

Trichloronitrosilbis (triphenylphosphine) ruthenium, dichlorobis (acetonitrile) bis (triphenylphosphine) ruthenium,

Dichlorobis (tetrahydrofuran) bis (triphenylphosphine) ruthenium,

Chlorohydride (toluene) tris (triphenylphosphine) ruthenium,

Chlorohydridecarbonyltris (triphenylphosphine) ruthenium,

Chlorohydridecarbonyltris (diethylphenylphosphine) ruthenium,

Chlorohydridenitrosiltris (triphenylphosphine) ruthenium,

Dichlorotris (trimethylphosphine) ruthenium, dichlorotris (triethylphosphine) ruthenium, dichlorotris (tricyclohexylphosphine) ruthenium,

Dichlorotris (triphenylphosphine) ruthenium,

Dichlorotris (trimethyldiphenylphosphine) ruthenium,

Dichlorotris (tridimethylphenylphosphine) ruthenium,

Dichlorotris (tri-o-tolylphosphine) ruthenium,

Dichlorotris (dichloroethylphosphine) ruthenium,

Dichlorotris (dichlorophenylphosphine) ruthenium,

Dichlorotris (trimethylphosphite) ruthenium,

And dichlorotris (triphenylphosphite) ruthenium.

Specific examples of the amine compound include secondary amine compounds such as methylamine, ethylamine, aniline, ethylenediamine, 1,3-diaminocyclobutane, dimethylamine, mailisopropylamine, and N-methylaniline. Tertiary amine compounds such as amine compounds, trimethylamine, triethylamine, triphenylamine, N, N-dimethylaniline, pyridine and γ-picolin, and the like, and preferably tertiary amine compounds are used, and in particular, When triethylamine is used, the hydrogenation rate is remarkably improved.

These organometallic complex or amine compound can be used together 2 or more types in arbitrary ratios, respectively.

When using a well-known hydrogenation catalyst which hydrogenates the ring-opening metathesis polymer in this invention, the usage-amount of a ring-opening metathesis polymer and a hydrogenation catalyst is a well-known hydrogenation catalyst with respect to a ring-opening metathesis polymer. It is 5-50000 ppm, Preferably it is 100-1000 ppm. In the case of using a hydrogenation catalyst composed of an organometallic complex and an amine compound, the organometallic complex is 5 to 50000 ppm, preferably 10 to 10000 ppm, particularly preferably 50 to 1000 ppm with respect to the ring-opening methesis polymer. . The amine compound is 0.1 to 1000 equivalents, preferably 0.5 to 500 equivalents, particularly preferably 1 to 100 equivalents, based on the organometallic complex to be used.

The hydrogenation catalyst composed of the organometallic complex and the amine compound may be used by contact treatment of the organometallic complex and the amine compound in advance. However, the organometallic complex and the amine compound may be added directly to the reaction system without first contacting the organometallic complex and the amine compound. do.

The solvent used in the hydrogenation reaction of the ring-opening metathesis polymer may be any solvent as long as it is a solvent normally used for the hydrogenation reaction, and the ring-opening metathesis polymer and its hydrogenated substance are dissolved, and the solvent itself is not hydrogenated. Solvents are preferred. For example, ethers, such as tetrahydrofuran, diethyl ether, dibutyl ether, or didimethoxyethane,

Aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene,

Aliphatic hydrocarbons such as pentane, hexane or heptane, aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or decalin, or

Halogenated hydrocarbons, such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, or trichlorobenzene, etc. are mentioned, These may mix and use 2 or more types.

The concentration of the hydrogenation reaction of the ring-opening metathesis polymer in the present invention is not the same depending on the ring-opening metathesis polymer, the hydrogenation catalyst and the type of the solvent, but the concentration of the ring-opening metathesis polymer with respect to the solvent is usually It is 0.01 g-10 kg / L, Preferably it is 0.1 g-5 kg / L, More preferably, it is the range of 0.5 g-1 kg / L.

In the hydrogenation reaction of the ring-opening metathesis polymer, the hydrogen pressure is usually in the range of normal pressure to 30 MPa, preferably 0.5 to 20 MPa, particularly preferably 2 to 15 MPa, and the reaction temperature is usually 0. It is the temperature of -300 degreeC, Preferably it is room temperature-250 degreeC, Especially preferably, it is the temperature range of 50-200 degreeC. The reaction time is usually 1 minute to 50 hours, preferably 10 minutes to 20 hours, and more preferably 30 minutes to 10 hours.

The ring-opening metathesis polymer hydrogenated product in the present invention can be dissolved in a solvent after isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution, but without isolating the ring-opening metathesis polymer. In addition, a method of performing a hydrogenation reaction by adding a hydrogenation catalyst comprising the organometallic complex and an amine compound may be employed.

After completion of the ring-opening metathesis polymerization or the hydrogenation reaction, the ring-opening metathesis catalyst or the hydrogenation catalyst remaining in the polymer can be removed by a known method. For example, filtration, adsorption by an adsorbent, an organic acid such as lactic acid, a poor solvent, and water are added to a solution containing a good solvent, and the system is extracted at room temperature or under heating. And a method of removing or washing and removing a solution or polymer slurry containing a good solvent by contact treatment with a basic compound and an acidic compound, and the like.

The method for recovering the polymer hydride from the ring-opened metathesis polymer hydrogenated solution is not particularly limited, and a known method can be used. For example, a method of discharging the reaction solution in a poor solvent under stirring and coagulating the polymer hydride, recovering it by centrifugation, decantation, etc., by blowing steam into the reaction solution to precipitate the polymer hydride The steam stripping method, the method of directly removing a solvent from a reaction solution by heating, etc. are mentioned.

When the hydrogenation method in the present invention is used, the hydrogenation rate can be easily achieved at 90% or more, and can be at least 95%, particularly at least 99%, and the cyclic olefin ring-opening metathesis thus obtained. The cisis polymer hydrogen additive becomes an excellent ring-opening metathesis polymer hydrogen additive without being easily oxidized.

The structure represented by structural unit [B] and / or general formula [4] which contain structural unit [A] represented by General formula [1] as needed by the above method as needed, and is represented by General formula [3]. A structural unit [E] containing at least a unit [C], represented by the general formula [7] as necessary, and a structural unit [F] represented by the general formula [22] as necessary, X ¹ of structural unit [A] represented by general formula [1], X ² of structural unit [B] represented by general formula [3], and X ³ of structural unit [C] represented by general formula [4] At least one is -O-, and its molar ratios [A] / ([B] and [C]) are from 0/100 to 99/1, preferably from 20/80 to 99/1, and the weight average molecular weight A ring-opening metathesis polymer hydrogenated additive having a ratio (Mw / Mn) between Mw and number average molecular weight Mn of 1.0 to 2.0 can be produced.

Moreover, in this invention, in the ring-opened metathesis polymer hydrogenated additive obtained as mentioned above, the tertiary ester group of cyclic alkyl in general formula [2], and / or the ester group in general formula [8] A structural unit represented by the structural unit [A] represented by the general formula [1] and the structural unit [B] and / or the general formula [4] represented by the general formula [1] by decomposing at least a part thereof to carboxylic acid [C], structural unit [D] represented by the general formula [5], structural unit [E] represented by the general formula [7] as necessary, and structural unit represented by the general formula [22] as necessary. X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], containing [F] and represented by the general formula [4] At least one of X ³ in the structural unit [C] is -O-, and its structural molar ratios [A] / ([B] and [C]) are 20/80 to 99/1, and the weight average molecular weight Mw and number Average minutes A ring-opening metathesis conjugated hydrogenated additive having a ratio (Mw / Mn) to self-weight Mn of 1.0 to 2.0 can be produced.

As a method of decomposing at least one part of the tertiary ester group of cyclic alkyl in General formula [2] and / or the ester group in General Formula [8], and converting it into carboxylic acid, it is a method by hydrolysis, and And / or acid decomposition may be used, and as hydrolysis, acidic hydrolysis, sodium hydroxide, hydroxide are carried out in the presence of an acidic catalyst such as sulfuric acid, hydrochloric acid, nitric acid, toluenesulfonic acid, trifluoroacetic acid or acetic acid. Any of alkaline hydrolysis performed in the presence of an alkaline catalyst such as potassium or barium hydroxide or neutral hydrolysis using sodium acetate, lithium iodide or the like instead of an acid or an alkaline catalyst can be used. In the method by hydrolysis, it is essential that water is present in the system, and the amount of water to be used is more than the molar amount of the ester group to be converted to carboxylic acid, preferably at least 5 mol times, more preferably at least 10 mol times, most preferably More than 20 moles. As the method by acid decomposition, acids, such as sulfuric acid, hydrochloric acid, nitric acid, toluenesulfonic acid, trifluoroacetic acid, or acetic acid, can be used. In the method by acid decomposition, water may be present in the system, but the presence of water is not essential. The amount of the acid catalyst used in the hydrolysis method, the alkaline catalyst, the neutral hydrolysis catalyst and the acid hydrolysis method is usually 50 moles or less with respect to 1 mole of the ester group converted to carboxylic acid, preferably 0.00001. It is the range of -30 mol, More preferably, it is the range of 0.001-10 mol.

The hydrolysis reaction and the acid decomposition reaction in the method of the present invention may use a water solvent or an organic solvent. Especially, as the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone, tetrahydrofuran and diethyl ether Ethers such as dibutyl ether, methoxy ethane, diionic acid, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, carboxylic acids such as acetic acid, nitromethane, etc. Pyrodines such as nitro compounds, pyridine and rutidine, and formamides such as dimethylformamide, and the like, and may be mixed with water or alcohols, or only organic solvents may be used. Moreover, you may mix and use these 2 or more types. The reaction temperature is usually 0 to 300 ° C, preferably room temperature to 250 ° C, more preferably room temperature to 200 ° C. The reaction time is usually 1 minute to 100 hours, preferably 5 minutes to 30 hours, and more preferably 10 minutes to 20 hours.

The embodiment of the hydrolysis reaction and the acid decomposition reaction in the method of the present invention is not particularly limited and may be in any form as long as it is a method capable of effectively carrying out the hydrolysis reaction and the acid decomposition reaction, under inert gas such as nitrogen. Moreover, even if it is under air, or may be any embodiment of pressure reduction, normal pressure, pressurization or ash, half ash, and continuous.

Moreover, you may neutralize suitably with an alkyl group or an acid after a hydrolysis reaction or an acid decomposition reaction. After the hydrolysis reaction or the acid decomposition reaction, the method of recovering the polymer from the ring-opened methacis polymer polymer hydrogenated solution or slurry is not particularly limited, and a known method can be used. For example, in the case of a solution, the reaction solution is discharged in a poor solvent under stirring to precipitate a polymer hydride to form a slurry, which is recovered by filtration, centrifugation, decantation, etc., by blowing steam into the reaction solution. The steam stripping method which precipitates a polymer, the method of removing a solvent directly from a reaction solution, etc. by heating etc. are mentioned, In the case of a slurry, the filtration method, the centrifugation method, the method of recovery by decantation, etc. are mentioned.

The structure represented by the structural unit [B] and / or general formula [4] which contain the structural unit [A] represented by General formula [1] as needed by the above method as needed, and is represented by General formula [3]. Unit [C], structural unit [D] represented by the general formula [5], structural unit [E] represented by the general formula [7] as necessary, and structural unit represented by the general formula [22] as necessary. It is represented by X ¹ of structural unit [A] represented by General Formula [1], X ² of structural unit [B] represented by General Formula [3] and containing [F]. At least one of X ³ of the structural unit [C] to be represented is -O-, and its molar ratios [A] / ([B] and [C]) are from 0/100 to 99/1, preferably from 20/80 to A ring-opening metathesis polymer hydrogenated additive having a ratio of 1.0 / 1 and a weight average molecular weight Mw and a number average molecular weight Mn (Mw / Mn) of 1.0 to 2.0 can be obtained.

Furthermore, in this invention, the structural unit [A] represented by General formula [1] is contained as needed by converting the carboxylic acid functional group of the ring-opening metathes polymerizable hydrogenated substance which has the carboxylic acid functional group obtained as mentioned above to ester, Structural unit [B] represented by general formula [3] and / or structural unit [C] represented by general formula [4], structural unit [D] represented by general formula [5] as necessary, and Therefore, the structural unit [E] represented by General Formula [7], and the structural unit [F] represented by General Formula [22] as necessary, and the structural unit [1] represented by General Formula [1] and a] of X ^1, the structural unit represented by the general formula [3] [B] X ² and represented by the general formula [structural unit [C] represented by the following 4] at least one of X ³ is -O-, its constituent The molar ratio [A] / ([B] and [C]) is 0/100 to 99/1, preferably 20/80 to 99/1, and the ratio (Mw) between the weight average molecular weight Mw and the number average molecular weight Mn / Mn) is 1.0 It can be prepared in a 2.0-opening metathesis polymer hydrogenation product.

As a method of converting a carboxylic acid functional group into an ester, a conventional method can be applied. For example, esterification by dehydration condensation with alcohols, esterification by ortho-alkylating agent, esterification by addition of olefins in the presence of acid, and condensation reaction with halides using organic base compounds. And esterification by alkoxy, or alkoxyalkyl esterification by addition of alkyl vinyl ethers. Moreover, after converting a carboxylic acid into an acid halide by thionyl chloride etc., the method of esterifying by contacting with alcohols, the method of esterifying by contacting a metal salt of carboxylic acid with a halide, etc. are mentioned.

As alcohols used in esterification by the dehydration condensation reaction with alcohols, any alcohol normally used for esterification can be used, for example, methanol, ethanol, 1-propanol, 2-propanol, 1- Butanol, 2-butanol, tert-butanol, 1-pentanol, tert-amyl alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, cyclopentanol,

Cyclopentanmethanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, cyclohexanol,

Cyclohexyl methanol, dicyclohexyl methanol, tricyclohexyl methanol,

1-methylcyclohexanol, norborneneol, 1-adamantanol, 2-adamantanol,

Aliphatic alcohols, such as 2-methyl-2-adamantanol and 1-adamantanemethanol, are preferable. The usage-amount of these alcohols is 100 mol or less normally with respect to 1 mol of carboxylic acids converted into ester, Preferably it is the range of 1-50 mol, More preferably, it is the range of 2-30 mol. Esterification by dehydration condensation with alcohols is usually carried out in the presence of an acid, and examples of such acids include inorganic acids such as hydrogen halides such as hydrogen chloride gas, sulfuric acid, phosphoric acid, hydrochloric acid, or hydrobromic acid, Solid acids such as heteropoly acid or Nafion ^R , p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid pyridine salt, trifluoroacetic acid pyridine salt, sulfuric acid pyridine salt or p-toluenesulfonic acid Organic acids, such as a pyridine salt, or Lewis acids, such as a boron trifluoride, etc. are mentioned. The usage-amount of these acids is 10 mol or less normally with respect to 1 mol of carboxylic acids converted into ester, Preferably it is the range of 0.00001-2 mol, More preferably, it is the range of 0.001-0.5 mol. Alternatively, a method of using an acidic ion exchange resin, for example, a method of solvent reflux using a soxhlet extractor containing a drying agent such as anhydrous magnesium sulfate or molecular sieve, for example, coexisting a dehydrating agent such as DCC Methods such as a method and a method using a large amount of alcohol can be used.

As the alkylating agent used in the esterification by ortho-alkylating agent, any alkylating agent usually used for esterifying carboxylic acid can be used, for example, diazoalkanes such as diazomethane, or, for example, ortho formic acid Orthocarboxylic acid trialkyls, such as triethyl or trimethyl ortho acetate, are preferable. The amount of the alkylating agent used is usually 50 moles or less, preferably 1 to 30 moles, with respect to 1 mole of the carboxylic acid to be converted into an ester. Preferably it is the range of 2-20 mol.

As olefins used in the etherification by addition of olefins in the presence of an acid, any of the olefins usually used for esterification can be used, for example, 2-methylpropene, 2-methyl-1 -Butene, 2-ethyl-1-butene, 2-methyl-2-butene, 3-methyl-2-pentene, 1-methyl-1-cyclopentene, 1-methyl-1-cyclohexene, methylenecyclopentane, methylene Aliphatic alkenes, such as cyclohexane and ethylidene cyclohexane, are preferable. The use amount of these olefins is 100 mol or less normally with respect to 1 mol of carboxylic acids converted into ester, Preferably it is the range of 1-50 mol, More preferably, it is the range of 2-30 mol. The esterification by addition of olefins is carried out in the presence of an acid, and as such an acid, for example, an inorganic acid such as hydrogen halide such as hydrogen chloride gas, sulfuric acid, phosphoric acid, hydrochloric acid or hydrobromic acid, heteropoly acid or Nafion ^R, etc. Organic acids such as solid acid, p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorsulfonic acid pyridine salt, or Lewis acids such as boron trifluoride. The usage-amount of these acids is 10 mol or less normally with respect to 1 mol of carboxylic acids converted into ester, Preferably it is the range of 0.00001-2 mol, More preferably, it is the range of 0.001-0.5 mol.

As alkyl vinyl ethers used in alkoxyalkyl esterification by addition of alkyl vinyl ethers, For example, methyl vinyl ether, ethyl vinyl ether,

n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,

sec-butyl vinyl ether, tert-butyl vinyl ether, isooctyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether,

tert-pentyl vinyl ether, octadecyl vinyl ether, cesyl vinyl ether,

2-methoxyethyl vinyl ether, vinyl-2- (2-ethoxyethoxy) ethyl ether,

Alkoxy substituted, unsubstituted or cyclic alkyl such as ethylene glycol butyl vinyl ether, tert-amyl vinyl ether, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, 1,4-dioxene, etc. Vinyl ethers are preferable. Among these, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2,3-dihydrofuran and 3,4-dihydro-2H-pyran are more preferable. The usage-amount of these alkyl vinyl ethers is 50 mol or less normally with respect to 1 mol of carboxylic acids converted into ester, Preferably it is the range of 1-30 mol, More preferably, it is the range of 2-20 mol.

The alkoxyalkyl esterification by addition of alkyl vinyl ethers is normally performed in presence of an acid, As such an acid, For example, inorganic acids, such as hydrogen halide, such as hydrogen chloride gas, sulfuric acid, phosphoric acid, hydrochloric acid, or hydrobromic acid, etc. Solid acids such as heteropoly acid or Nafion ^R , or p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid pyridine salt, trifluoroacetic acid pyridine salt, p-toluenesulfonic acid pyridine salt Or sulfuric acid pyridine salt etc. are mentioned, Among these, it is preferable to use hydrogen chloride gas, hydrochloric acid, a trifluoroacetic acid, a trifluoroacetic acid pyridine salt, p-toluenesulfonic acid pyridine salt, or a sulfuric acid pyridine salt. . These acids may be used alone or in combination of two or more, or may be used simultaneously or sequentially. The usage-amount of these acid catalysts is 10 mol or less normally with respect to 1 mol of carboxylic acids converted into ester, Preferably it is the range of 0.00001-2 mol, More preferably, it is the range of 0.001-0.5 mol.

A solvent is usually used for the method of converting a carboxylic acid functional group into ester in the method of this invention. These solvents may not be the same depending on the method to be used or the kind of the ester to be used, and either or both of an aqueous solution or an organic solution may be used. Particularly, as the organic solvent to be used, alcohols such as methanol and ethanol, ketones such as acetone and tetra Ethers such as hydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, decalin, Halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, chlorobenzene, orthodichlorobenzene, carboxylic acids such as acetic acid, nitro compounds such as nitromethane, pyridines such as pyridine and lutidine, and forms such as dimethylformamide Amides etc. can be mentioned, You may mix with water or alcohol, and only an organic solvent It is solubility. Moreover, you may mix and use these 2 or more types. Reaction temperature is 0-200 degreeC normally, Preferably it is 10-150 degreeC, More preferably, it is room temperature-200 degreeC, Reaction time is 1 minute-100 hours normally, More preferably, it is 5 minutes-30 hours. More preferably, it is the range of 10 minutes-20 hours.

The embodiment of the method for converting the carboxylic acid functional group into the ester in the method of the present invention is not particularly limited, and may be in any form as long as it is a method capable of effectively converting the carboxylic acid functional group to the ester, and inert gas such as nitrogen Under air, under air, or under reduced pressure, atmospheric pressure, pressurized or batch, semi-batch, continuous mode may be sufficient.

Moreover, after ester conversion of a carboxylic acid functional group, you may neutralize suitably with alkali or an acid. After converting the carboxylic acid functional group to an ester, the method of recovering the polymer from the ring-opened methacis polymer polymer hydrogenated solution or slurry is not particularly limited, and a known method can be used. For example, in the case of a solution, the reaction solution is discharged into a poor solvent under stirring to precipitate a polymer hydride into a slurry, which is recovered by filtration, centrifugation, decantation, or the like, and the polymer is formed by blowing steam into the reaction solution. The steam stripping method to precipitate, the method of removing a solution directly from a reaction solution by heating, etc. are mentioned, In the case of a slurry, the method of collect | recovering by a filtration method, a centrifugation method, a decantation method, etc. are mentioned directly.

The structure represented by structural unit [B] and / or general formula [4] which contain structural unit [A] represented by General formula [1] as needed by the above method as needed, and is represented by General formula [3]. Unit [C], structural unit [D] represented by general formula [5] as needed, structural unit [E] represented by general formula [7] as needed, and general formula [22] as needed. X ² and general formula [of structural unit [B] represented by structural unit [A, X ¹ , general formula [3], containing structural unit [F] represented by At least one of X ³ in the structural unit [C] represented by 4] is -O-, and its molar ratios [A] / ([B] and [C]) are 1/100 to 99/1, preferably A ring-opening metathesis polymer hydrogenated additive having a ratio (Mw / Mn) of 20/80 to 99/1 and a weight average molecular weight Mw and a number average molecular weight Mn is 1.0 to 2.0.

The ring-opening metathesis polymer hydrogenated additive in the present invention is useful as a base polymer for photoresist. For example, it is used as a positive resist composition with an acid generator and a solvent. The acid generator is a substance that generates Bronsted acid or Lewis acid when exposed to activating radiation. In addition, a dissolution rate modifier, a surfactant, a storage stabilizer, a sensitizer, or a striation inhibitor may be added to the resist composition. The resist composition can be formed by, for example, applying the composition to a substrate surface such as a silicon wafer by spin coating or the like, and then forming a resist film by drying and removing the solvent. , Ultraviolet rays, KrF excimer laser, ArF excimer laser, and electron beam are irradiated to the resist film, and heat treatment (post-exposure bake) can further increase the sensitivity. Subsequently, a relief pattern is obtained by wash | cleaning an exposed part with developing solutions, such as aqueous alkali solution. The relief pattern formed using the ring-opening metathesis polymer hydrogenated additive of the present invention has extremely good resolution and contrast. Alternatively, the substrate may be etched using the pattern formed as described above as a mask.

In the present invention, the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [2] and / or the structure of the structural unit [C] represented by the general formula [4] The molar ratio [A] / ([B] and [C]) of the unit is 20/80 to 99/1. Here, the structural unit [A] contains a tertiary ester group of cyclic alkyl which is decomposed by an acid generated from a photosensitive agent at the time of exposure, and is required to develop a resist pattern by developing with alkaline aqueous solution after exposure. Units [B] and [C] are necessary for expressing adhesiveness with a substrate to be processed, such as a silicon substrate. If these molar ratios [A] / ([B] and [C]) are less than 20/80, the development becomes insufficient, and if it exceeds 99/1, the adhesion with the substrate to be processed is not expressed. Moreover, the structural unit [D] represented by General formula [6] contains a carboxylic acid group, can improve adhesiveness with the to-be-processed board | substrates, such as a silicon substrate, and can improve solubility to a solvent. Furthermore, the molar ratio ([A] + [B] + [C]) / [D] of the structural units [A], [B] and [C] and the structural units [D] is 100/0 to 20 / When it exists in the range of 80, it is preferable to improve the wetting tension at the time of image development by the alkaline aqueous solution after exposure, and to solve image development stain. These structural units are in this range, which are suitable for preparing a resist composition, are dissolved in a polar solvent such as 2-heptanone together with a highly polar photosensitive agent, and are used on a substrate to be treated such as a silicon substrate. It is extremely important as a resist material to apply | coat. That is, when the ring-opening metathesis polymer hydrogenated additive prepares the resist composition, it is possible to form a uniform smooth coating film by increasing the solubility or dissolution rate in the polar solvent. Moreover, if structural unit [E] is contained in addition to structural unit [A], [B], and / or [C], it will contain ester group different from reactivity with ester group contained in structural unit [A], and therefore exposure This is useful because the resolution of the city can be freely controlled. The molar ratio ([A] + [B] + [C]) / [E] of the preferred structural unit in this case is in the range of 100/0 to 40/60.

In particular, X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3] and the structural unit [C] represented by the general formula [4] The ring-opening metathesis polymer hydrogenated substance having at least one of X ³ and -O ₂ and -CH ₂ -has an adhesion property to a substrate to be treated such as a silicon substrate and a wettability at the time of development by alkaline aqueous solution. There is an effect of further improving solubility in polar organic solvents, such as ketones and alcohols, used in the process of improving and applying to a silicon wafer of a resist agent. Moreover, the affinity with respect to water also improves, and the developability with respect to the peeling agent (or developer), such as alkaline aqueous solution after exposure, also improves.

Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited by these.

In addition, the physical property value of the polymer obtained in the Example was measured by the following method.

Average molecular weight: GPC was used to dissolve the obtained cyclic olefin ring-opening metathesis polymer, hydrogenated product of this polymer in tetrahydrofuran, and as a detector 830-RI and 875-UV, manufactured by Nippon Bunko Corp., Japan as a detector. The molecular weight was corrected by polystyrene standards using Shodex k-805, 804, 803, and 802.5 at a flow rate of 1.0 ml / min at room temperature.

Hydrogenation rate: The cyclic olefin ring-opened metathesis polymer hydrogenated powder was dissolved in deuterated chloroform and subjected to carbon-carbon double bond of δ = 4.0 to 6.5 ppm main chain using 270 MHz- ¹ HNMR. The peak attributing calculated the magnitude | size which decreases by a hydrogenation reaction.

Ratio of carboxylic acid contained in a polymer: It measured by neutralization titration which uses bromothymol blue as an indicator.

UV Absorption Spectrum: Using a spin coater on a quartz glass plate, the film was applied at a rotational speed of 3000 rpm at a film thickness of 1.0 mu m, and the UV absorption spectrum was measured by UV-3100 manufactured by Shimadzu Corporation, Japan.

Adhesion to Silicon Wafer Substrate: Similarly, the solution is applied to the substrate with a spin coater, the obtained polymer film is baked at 120 ° C. for 10 minutes, scratched on a lattice pattern according to the test method of JIS D0202, and peeled off with a cellophane adhesive tape. The peeled state was visually observed.

Judgment is made with: peeling less than 5%, :: peeling less than 5 to 20%,?: Peeling less than 20 to 50%, and ×: peeling at 50% or more.

Example 1

3,6-epoxy-1,2,3,6-tetrahydrophthalide (2.43 g, 16 mmol) and 8- (1'-ethylcyclophene) as cyclic olefin monomers in a 300 ml Schlenk flask under nitrogen atmosphere. Methoxy) sarbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (7.21 g, 24 mmol) was dissolved in tetrahydrofuran (hereinafter referred to as "THF"). W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OC (CF ₃ ) ₂ Me) ₂ (PMe ₃ ) (462 mg, 0.57 mmol) was added to this as a ring-opening metathesis polymerization catalyst. The reaction was carried out for 1 hour at room temperature. Thereafter, butylaldehyde (205 mg, 2.85 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, filtered, washed with methanol, and dried in vacuo to obtain 9.46 g of the ring-opened metathesis polymer powder.

Thereafter, 9.0 g of this ring-opening metathesis polymer powder was dissolved in THF (100 ml) in a 200 ml autoclave, and dichlorotetrakis (triphenylphosphine) ruthenium (27 mg, 0.022 mmol) prepared in advance as a hydrogenation catalyst. And THF (20 mL) solution of triethylamine (11.3 mg, 0.108 mmol) were added and hydrogenated at a hydrogen pressure of 8.1 MPa at 165 DEG C for 5 hours, and then the temperature was returned to room temperature to release hydrogen gas. I was. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, and then separated by filtration, followed by vacuum drying to obtain 8.0 g of a white powdered ring-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive did not identify the peak which belongs to the proton of the olefin of a main chain, and the hydrogenation rate was 100%, and the polystyrene standard conversion measured by GPC The number average molecular weight Mn was 37,600 and Mw / Mn was 1.10. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 60/40. ¹ H-NMR spectrum (270 MHz, in which the solvent is deuterated chloroform) of the ring-opening metathesis polymer hydrogenated product obtained in Example 1 is shown in FIG. 1.

Example 2

In Example 1, the cyclic olefin monomer was prepared as 6,9-methylene-2-oxaspiro [4,5] 7-decen-1-one (1.31 g, 8 mmol), 3,6-epoxy-1,2,3 , 6-tetrahydrophthalide (1.83g, 12mmol) and 8- (1'-ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (6.01g, 20mmol) A ring-opening metathesis polymerization was conducted in the same manner as in Example 1 except that the ring-opening metathesis polymer was obtained.

Further, 9.0 g of the obtained ring-opened metathesis polymer powder was subjected to a hydrogenation reaction at a hydrogen pressure of 8.1 MPa and a temperature of 165 ° C. for 5 hours in the same manner as in Example 1, to obtain 8.4 g of a white powder-opened metathesis polymer hydrogenated product. The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive did not identify the peak which belongs to the proton of the olefin of a main chain, and the hydrogenation rate was 100%, and the polystyrene standard conversion measured by GPC The number average molecular weight Mn was 35,600 and Mw / Mn was 1.20. Moreover, the composition ratio of the structural unit [A] / [B] / [C] of the obtained polymer was 50/30/20.

Example 3

In Example 1, the ring-opening metathesis polymerization catalyst was changed to Mo (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC (CF ₃ ) ₂ Me) ₂ (198 mg, 0.286 mmol) A ring-opening metathesis polymerization was carried out in the same manner as in Example 1 except that the ring-opening metathesis polymer of 9.25 g was obtained.

Subsequently, 9.0 g of the ring-opening metathesis polymer powder was dissolved in THF (100 ml) in a 200 ml autoclave, and chlorohydrylcarbonyltris (triphenylphosphine) ruthenium (27 mg, prepared in advance as a hydrogenation catalyst) 0.022 mmol) and THF (20 mL) solution of triethylamine (11.3 mg, 0.108 mmol) were added thereto, followed by hydrogenation at a hydrogen pressure of 8.1 MPa and a temperature of 165 ° C. for 5 hours. The gas was released. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated product, separated by filtration, and vacuum-dried to obtain 8.1 g of a white powder-opened metathesis polymer hydrogenated product. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive did not confirm the peak which belongs to the proton of the olefin of a main chain, and the hydrogenation rate was 100%, and polystyrene standard conversion measured by GPC The number average molecular weight of Mn was 75,200 and Mw / Mn was 1.15. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 60/40.

Example 4

The ring-opening metathesis in Example 2 was changed in the same manner as in Example 2 except that the ring-opening metathesis polymerization catalyst was changed to Ru (P (C ₆ H ₁₁ ) ₃ ) ₂ (CHPh) Cl ₂ (470 mg, 0.57 mmol). The polymerization was carried out to obtain 9.0 g of a ring-opening metathesis polymer.

Further, 9.0 g of the obtained ring-opened metathesis polymer powder was subjected to a hydrogenation reaction at a hydrogen pressure of 8.0 MPa and a temperature of 165 ° C. for 5 hours in the same manner as in Example 2, to obtain 8.6 g of a white powder-opened methesis polymer hydrogenated additive. The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive did not confirm the peak which belongs to the proton of the olefin of a main chain, and the hydrogenation rate was 100%, and polystyrene standard conversion measured by GPC The number-average molecular weight Mn was 33,100 and Mw / Mn was 1.37. Moreover, the composition ratio of the structural unit [A] / [B] / [C] of the obtained polymer was 50/30/20.

Example 5

Under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (17.0 g, 111.7 mmol) and 8- (as a cyclic olefin monomer were placed in a 1000 ml autoclave equipped with a magnetic stirrer. 1'-ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (33.57 g, 111.7 mmol) was dissolved in tetrahydrofuran (550 mL). 1,5-hexadiene (1.5 ml, 12.3 mmol) as a chain transfer agent and Mo (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC (CF ₃ ) as a ring-opening metathesis polymerization catalyst. ) ₂ Me) ₂ (786 mg, 1.12 mmol) was added and reacted at room temperature for 2 hours. Thereafter, butylaldehyde (404 mg, 5.60 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, filtered, washed with methanol, and dried in vacuo to obtain 42.5 g of the ring-opened metathesis polymer powder.

Subsequently, 40.0 g of this ring-opening metathesis polymer powder was dissolved in THF (400 ml) in a 1000 ml autoclave, and chlorohydrylcarbonyltris (triphenylphosphine) ruthenium (20 mg, prepared in advance as a hydrogenation catalyst). 0.02 mmol) of THF (20 mL) was added, and hydrogenated at a hydrogen pressure of 6.0 MPa at a temperature of 100 ° C. for 20 hours, and then the temperature was returned to room temperature to release hydrogen gas. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, separated by filtration, and dried in vacuo to obtain 38.5 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive did not identify the peak which belongs to the proton of the olefin of a main chain, and the hydrogenation rate was 100%, and the polystyrene standard conversion measured by GPC The number average molecular weight Mn was 8260 and Mw / Mn was 1.32. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 50/50.

Example 6

Under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrodimethylphthalide (11.41 g, 75.0 mmol) and 8- () were used as a cyclic olefin monomer in a 1000 ml autoclave equipped with a magnetic stirrer. 2'-ethyl-2'-norbornyloxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (36.73 g, 112.5 mmol) was dissolved in tetrahydrofuran (500 mL). 1,6-heptadiene (3.17 mL, 23.41 mmol) as a chain transfer agent and W (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC (CF ₃ ) as a ring-opening metathesis polymerization catalyst. ) ₂ Me) ₂ (740 mg, 0.935 mmol) was added thereto and reacted at room temperature for 3 hours. Thereafter, butylaldehyde (360 mg, 5.00 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 48.9 g of the ring-opening metathesis polymer powder.

Subsequently, 40.0 g of this ring-opening metathesis polymer powder and 5% palladium carbon (5.0 g, 2.35 mmol as palladium) were added to a 500 ml autoclave, and a hydrogen pressure of 8.0 MPa was added. After the hydrogenation reaction was performed at a temperature of 120 ° C. for 24 hours, the temperature was returned to room temperature to release hydrogen gas. After removing the palladium carbon used as a catalyst by filtration, this ring-opened metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, separated by filtration, and dried in vacuo to form a white powder. 39.1g of the ring-opening metathesis polymer hydrogenated substance was obtained. The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 99%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 4690, and Mw / Mn was 1.38. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 60/40.

Example 7

Under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydromonomethyl phthalide (19.94 g, 120.0 mmol) and 8- as a cyclic olefin monomer were placed in a 1000 ml autoclave equipped with a magnetic stirrer. (2'-ethyl-2'-adamantyloxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (28.20 g, 80.0 mmol) was dissolved in toluene (600 mL). To this was added 1-octene (10.3 ml, 65.0 mmol) as a chain transfer agent and Re (CBU ^t ) (CHBU ^t ) (OC (CF ₃ ) ₂ Me) ₂ (687.6 mg, 1.00 mmol) as a ring-opening metathesis polymerization catalyst. It was added and reacted at 50 degreeC for 6 hours. Thereafter, butylaldehyde (360 mg, 5.00 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 46.3 g of the ring-opening metathesis polymer powder.

Subsequently, 40.0 g of this ring-opening metathesis polymer powder was added to a 1000 ml autoclave, dihydride tetrakis (triphenylphosphine) ruthenium (12.0 mg, 0.013 mmol), triethylamine (4.05 mg, 0.04 mmol) and toluene (600 ml) were added as a solvent, hydrogenated at a hydrogen pressure of 8.0 MPa at a temperature of 100 DEG C for 24 hours, and then the temperature was returned to room temperature to release hydrogen gas. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, separated by filtration, and vacuum-dried to obtain 38.8 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenation additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 2880, and Mw / Mn was 1.42. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 40/60.

Example 8

20.0 g of the ring-opened metathesis polymer hydrogenated additive obtained in Example 5 was added to a 1000 ml solution of 5.0 ml of toluene of 5.0 ml of trifluoroacetic acid in a 2000 ml eggplant flask, stirred at 70 ° C. for 3 hours, and then the solvent was removed again. It was dissolved in THF, added to methanol, precipitated, filtered, and dried in vacuo to obtain 17.8 g of a ring-opened metathesis polymer hydrogenated product which was partially esterified in the form of a white powder. The composition ratio of the structural unit [A] / [B] / [C] of the obtained polymer was 30/50/20, the number average molecular weight Mn measured by GPC was 8150, and Mw / Mn was 1.33.

Example 9

15.0 g of the ring-opened metathesis polymer hydrogenated additive obtained in Example 6 was added to a 1000 ml solution of 5.0 ml of trifluoroacetic acid in a 2000 ml eggplant flask, stirred at 70 ° C. for 2 hours, and then the solvent was removed again. It was dissolved in THF, added to methanol, precipitated, filtered, and vacuum dried to obtain 13.1 g of a ring-opened metathesis polymer hydrogenated product which was partially esterified in the form of a white powder. The composition ratio of the structural unit [A] / [B] / [D] of the obtained polymer was 40/40/20, the number average molecular weight Mn measured by GPC was 4490 and Mw / Mn was 1.35.

Example 10

15.0 g of the ring-opened metathesis polymer hydrogenated additive obtained in Example 7 was added to a 1000 ml solution of 10.0 ml of concentrated hydrochloric acid in a 2000 ml eggplant flask, stirred at 60 ° C. for 6 hours, added to methanol, precipitated and filtered. It dried and vacuum-dried and obtained the 13.0g of ring-opening metathesis polymer hydrogenated additive which partially ester-decomposed the white powder shape. The composition ratio of the structural unit [A] / [B] / [D] of the obtained polymer was 25/60/15, the number average molecular weight Mn measured by GPC was 2810 and Mw / Mn was 1.39.

Example 11

In a 500 ml autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (9.89 g, 65.0 mmol) and 8- ( 1'-ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (11.72 g, 39.0 mmol) and 8-tert-butoxycarbonyltetracyclo [4.4.0.12, 5.17 , 10] -3-dodecene (6.77 g, 26.0 mmol) was dissolved in 300 ml of tetrahydrofuran. 1,5-hexadiene (0.75 ml, 6.5 mmol) as a chain transfer agent and Mo (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OC (CF) as a ring-opening metathesis polymerization catalyst. ₃ ) ₂ Me) ₂ (536 mg, 0.70 mmol) was added thereto and reacted at room temperature for 2 hours. Thereafter, butylaldehyde (250 mg, 3.47 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 26.6 g of the ring-opening metathesis polymer powder.

Thereafter, 20.0 g of this ring-opening metathesis polymer powder was dissolved in THF (300 ml) in a 500 ml autoclave, and dichlorotris (triphenylphosphine) onium (30.0 mg, 0.029 mmol) prepared in advance as a hydrogenation catalyst. Then, THF (20 mL) solution of triethylamine (11.74 mL, 0.116 mmol) was added thereto, followed by hydrogenation at a hydrogen pressure of 6.0 MPa at 100 占 폚 for 2 hours, and then the temperature was returned to room temperature to release hydrogen gas. I was. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated product, and the resultant was vacuum-dried after separation by filtration to obtain 18.8 g of a white powder-opened metathesis polymer hydrogenated product. The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 9110, and Mw / Mn was 1.43. Moreover, the composition ratio of the structural unit [A] / [B] / [E] of the obtained polymer was 30/50/20.

Example 12

In a 500 ml autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (9.13 g, 60.0 mmol) and 8- ( 1'-ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (14.42 g, 48.0 mmol) and 8-methoxycarbonyltetracyclo [4.4.0.12, 5.17, 10 ] -3-dodecene (2.62 g, 12.0 mmol) was dissolved in 350 ml of toluene. 1,5-hexadiene (0.70 ml, 6.0 mmol) as a chain transfer agent and W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OC (CF ₃ ) as a ring-opening metathesis polymerization catalyst. ) ₂ Me) ₂ (440 mg, 0.60 mmol) was added thereto and reacted at room temperature for 5 hours. Thereafter, butylaldehyde (216 mg, 3.0 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 24.7 g of the ring-opening metathesis polymer powder.

Then, 20.0 g of this ring-opening metathesis polymer powder was dissolved in toluene (350 ml) in a 500 ml autoclave, and dichlorobis (triphenylphosphine) palladium (66.0 mg, 0.094 mmol) toluene (66.0 mg, 0.094 mmol) was added as a hydrogenation catalyst. 30 ml) was added, and hydrogenated at a hydrogen pressure of 6.0 MPa at a temperature of 100 DEG C for 20 hours, and then the temperature was returned to room temperature to release hydrogen gas. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, which was separated by filtration, and then dried in vacuo to give 17.9 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 8810, and Mw / Mn was 1.24. Moreover, the composition ratio of the structural unit [A] / [B] / [E] of the obtained polymer was 40/50/10.

Example 13

9.0 g of the ring-opened metathesis polymer hydrogenated additive obtained in Example 12 was added to a solution in 400 ml of 5% potassium hydroxide methanol solution in a 1000 ml eggplant flask, stirred at 80 ° C. for 3 hours, and thereafter, 1000 ml of 2% aqueous hydrochloric acid solution. It was added to mL, neutralized, precipitated, filtered, washed with water, and dried in vacuo to obtain 8.4 g of a partially hydrolyzed ring-opened metathesis polymer hydrogenated additive in the form of a white powder. The composition ratio of structural unit [A] / [B] / [D] of the obtained polymer was 40/50/10, the number average molecular weight Mn measured by GPC was 8730, and Mw / Mn was 1.25.

Example 14

In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (9.13 g, 60.0 mmol) and 8- ( 1'-ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (9.01 g, 30.0 mmol) and 8- (tetrahydropyran-2'-yl) oxycarbonyltetra Cyclo [4.4.0.1 ^2.5 .1 ^7.10 ] -3-dodecene (8.65 g, 30.0 mmol) was dissolved in 320 mL of THF. 1,5-hexadiene (0.70 ml, 6.0 mmol) as a chain transfer agent and W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OBU ^t ) ₂ as ring-opening metathesis polymerization catalyst (PMe ₃ ) (356 mg, 0.60 mmol) was added and reacted at room temperature for 5 hours. Thereafter, butylaldehyde (216 mg, 3.0 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 24.3 g of the ring-opening metathesis polymer powder.

Then, 20.0 g of this ring-opening metathesis polymer powder was dissolved in THF (300 ml) in a 500 ml autoclave, and THF (91.0 mg, 0.10 mmol) of chlorotris (triphenylphosphine) rhodium (91.0 mg, 0.10 mmol) was added as a hydrogenation catalyst. 30 ml) was added, and hydrogenated at a hydrogen pressure of 6.0 MPa at a temperature of 100 DEG C for 20 hours, and then the temperature was returned to room temperature to release hydrogen gas. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, which was separated by filtration, and then vacuum dried to obtain 17.1 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 9620, and Mw / Mn was 1.19. Moreover, the composition ratio of the structural unit [A] / [B] / [E] of the obtained polymer was 25/50/25.

Example 15

8.0 g of the ring-opening metathesis polymer hydrogenated additive obtained in Example 14 was added to a 500 ml solution of 3.0 ml of trifluoroacetic acid 3.0 ml in a 1000 ml eggplant flask, stirred at 30 ° C for 1 hour, and the solvent was distilled off. The resultant was dissolved in THF, added to methanol, precipitated, filtered and dried in vacuo to give 6.8 g of white powder. As a result of NMR analysis, only the tetrahydropyranyl group was the ester-opening metathesis polymer hydrogenated product. The composition ratio of the structural unit [A] / [B] / [D] of the obtained polymer was 25/50/25, the number average molecular weight Mn measured by GPC was 9060 and Mw / Mn was 1.21.

Example 16

In a 500 ml three-necked branched flask equipped with a 100 ml dropping funnel, a stirrer and a three-way cock, 8.0 g of partially etherified ring-opened metathesis polymer hydrogenated additive obtained in Example 8 under a nitrogen atmosphere was p. A 200 ml solution of toluene of 80 mg of toluenesulfonic acid pyridine salt was added, and a 70 ml solution of 5,6-dihydropyran (10 g) of toluene was added dropwise for about 1 hour while stirring at 25 ° C. It stirred at 2 hours. After removal of the solvent, it was dissolved in THF, added to methanol, precipitated, filtered, and dried in vacuo to yield 6.6 g of a partially powdered ring-opened metathesis polymer hydrogenated additive in the form of a white powder. The composition ratio of the structural units [A] / [B] / [D] / [E] of the obtained polymer was 30/50/5/15, the number average molecular weight Mn measured by GPC was 8200, and Mw / Mn was 1.33. .

Example 17

In a 500 ml autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 4-oxatricyclo [5.2.1.0 ^2.6 ] dec-8-en-3-one (4.51 g, 30.0 mmol) and 8- as cyclic olefin monomers were used. (1'-Ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (12.02 g, 40.0 mmol) and 5- (1'-ethylcyclopentoxy) carbonyl-6 -Methoxycartyl-7-oxabicyclo [2.2.1] hept-2-ene (8.83 g, 30.0 mmol) was dissolved in 350 mL THF. 1-hexene (0.42 ml, 3.5 mmol) as a chain transfer agent and W (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OBU ^t ) ₂ (288 mg) as a ring-opening metathesis polymerization catalyst , 0.50 mmol) was added and reacted at room temperature for 5 hours. Thereafter, butylaldehyde (180 mg, 2.5 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 23.3 g of the ring-opening metathesis polymer powder.

Thereafter, 20.0 g of this ring-opening metathesis polymer powder was dissolved in THF (500 ml) in a 1000 ml autoclave, and dichlorobis (tetrahydrofuran) bis (triphenylphosphine) ruthenium (prepared as a hydrogenation catalyst) 4.0 mg, 0.0048 mmol) and THF (100 mL) solution of triethylamine (4.86 mg, 0.048 mmol) were added, and after hydrogenation reaction was performed at a hydrogen pressure of 6.0 MPa at 100 ° C. for 20 hours, the temperature was adjusted to room temperature. The gas was returned to release hydrogen gas. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, which was separated by filtration, and then vacuum dried to obtain 18.1 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer-hydrogen additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 12600, and Mw / Mn was 1.39. Moreover, the composition ratio of the structural unit [A] / [A] '/ [E] of the obtained polymer was 40/30/30.

Example 18

In a 500 ml autoclave equipped with a magnetic stirrer under nitrogen atmosphere, 5-oxapentacyclo [7.4.0.0 ^3.7 .1 ^2.8 .1 ^{10 13} ] -pentadidec-11-en-4-one ( 10.81 g, 50.0 mmol) and 5- (1'-ethylcyclopentoxy) carbonyl-7-oxabicyclo [2.2.1] hept-2-ene (11.82 g, 50.0 mmol) were dissolved in 250 mL THF. . 1-heptene (0.64 ml, 6.5 mmol) as a chain transfer agent and W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OBU ^t ) ₂ (PMe ₃ ) as a ring-opening metathesis polymerization catalyst. (328 mg, 0.50 mmol) was added and reacted at room temperature for 5 hours. Thereafter, pentyl aldehyde (258 mg, 3.0 mmol) was added, the mixture was stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing, and vacuum drying to obtain 20.8 g of the ring-opening metathesis polymer powder.

Subsequently, 15.0 g of this ring-opening metathesis polymer powder was dissolved in THF (300 ml) in a 500 ml autoclave, and chlorohydride carbonyl tris (triphenylphosphine) ruthedium (9.5) prepared as a hydrogenation catalyst in advance. Mg, 0.01 mmol) and a THF (30 mL) solution of triethylamine (4.9 mg, 0.02 mmol) were added, and after hydrogenation reaction was carried out at a hydrogen pressure of 10.0 MPa and a temperature of 80 ° C for 42 hours, the temperature was returned to room temperature. Hydrogen gas was released. This ring-opened metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, separated by filtration, and vacuum-dried to obtain 12.3 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 8450, and Mw / Mn was 1.29. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 50/50.

Example 19

In a 500 ml autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (11.41 g, 75.0 mmol) and 8- ( 1'-ethylcyclopentoxy) carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (7.51 g, 25.0 mmol) and 8- (2'-ethyl-2'-norbornyloxy) Carbonyltetracyclo [4.4.0.12, 5.17, 10] -3-decene (8.16 g, 25.0 mmol) was dissolved in 300 mL of THF. 1,5-hexadiene (1.04 mL, 9.0 mmol) as a chain transfer agent. And W (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OBU ^t ) ₂ (PMe ₃ ) (652mg, 1.00mmol) as ring-opening metathesis polymerization catalyst for 5 hours at room temperature. Reacted. Thereafter, butylaldehyde (432 mg, 6.0 mmol) was added thereto, stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 25.1 g of the ring-opening metathesis polymer powder.

Subsequently, 10.0 g of this ring-opening metathesis polymer powder was dissolved in THF (350 ml) in a 1000 ml autoclave, and dichlorotris (trimethylphosphate) ruthenium (44.8 mg, 0.10 mmol) and triethyl prepared in advance as a hydrogenation catalyst. A THF (200 mL) solution of amine (15.2 mL, 0.15 mmol) was added, and hydrogenated at 10.0 MPa hydrogen and 70 ° C. for 20 hours, and then the temperature was returned to room temperature to release hydrogen gas. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, which was separated by filtration and dried under vacuum to obtain 8.8 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 8330, and Mw / Mn was 1.44. Moreover, the composition ratio of the structural unit [A] / [A] '/ [B] of the obtained polymer was 20/20/60.

Example 20

3,6-epoxy-1,2,3,6-tetrahydrophthalide (2.43 g, 16 mmol) and 8- (1'-ethylcyclophene) as cyclic olefin monomers in a 500 ml Schlenk flask under a nitrogen atmosphere. Methoxy) carbonyl-8-methyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (7.55 g, 24 mmol) was dissolved in 200 ml of tetrahydrofuran. W (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OC (CF ₃ ) ₂ Me) ₂ (PMe ₃ ) (606 mg, 0.70 mmol) was used as a ring-opening metathesis polymerization catalyst. The reaction was carried out for 30 hours at room temperature. Thereafter, butyl aldehyde (202 mg, 2.80 mmol) was added, the mixture was stirred for 1 hour, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, filtered, washed with methanol, and dried in vacuo to obtain 9.13 g of the ring-opened metathesis polymer powder.

Thereafter, 9.0 g of this ring-opening metathesis polymer powder was dissolved in THF (250 ml) in a 500 ml autoclave, and dichlorotetrakis (triphenylphosphine) ruthenium (27 mg, 0.022 mmol) prepared in advance as a hydrogenation catalyst. And THF (50 mL) solution of triethylamine (11.3 mg, 0.108 mmol) were added thereto, followed by hydrogenation reaction at a hydrogen pressure of 9.0 MPa and a temperature of 120 ° C. for 16 hours, and then the temperature was returned to room temperature to release hydrogen gas. I was. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, separated by filtration, and vacuum-dried to obtain 7.4 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 28,600, and Mw / Mn was 1.07. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 60/40.

Example 21

In a 500 ml Schlenk flask under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (4.56 g, 30.0 mmol) and 8-[(1'-ethyl) were used as cyclic olefin monomers. Cyclopentoxy) carbonylmethylene] tetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (6.29 g, 20.0 mmol) was dissolved in 200 ml of tetrahydrofuran. W (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OC (CF ₃ ) ₂ Me) ₂ (PMe ₃ ) (606 mg, 0.70 mmol) was used as a ring-opening metathesis polymerization catalyst. The reaction was carried out for 30 minutes at room temperature. Thereafter, butyl aldehyde (202 mg, 2.80 mmol) was added, the mixture was stirred for 1 hour, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, filtered, washed with methanol and dried in vacuo to obtain 9.98 g of the ring-opened metathesis polymer powder.

Subsequently, 9.0 g of this ring-opening metathesis polymer powder was dissolved in toluene (250 ml) in a 500 ml autoclave, and dichlorotetrakis (triphenylphosphine) ruthenium (61 mg, 0.05 mmol) prepared in advance as a hydrogenation catalyst. And THF (50 mL) solution of triethylamine (10.1 mg, 0.10 mmol) were added thereto, followed by hydrogenation at a hydrogen pressure of 9.0 MPa at 90 ° C. for 16 hours, and then the temperature was returned to room temperature to release hydrogen gas. I was. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, and then separated by filtration, followed by vacuum drying to obtain 8.0 g of a white powdered ring-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenation additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 34,100, and Mw / Mn was 1.09. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 40/60.

Example 22

In a 500 ml Schlenk flask under nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrodimethylphthalide (1.08 g, 6.0 mmol) and 8,9-[(1 ') were used as cyclic olefin monomers. -Ethylcyclopentoxy) carbonyl] tetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (6.17 g, 14.0 mmol) was dissolved in 200 ml of tetrahydrofuran. To this was added Mo (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OC (CF ₃ ) ₂ Me) ₂ (206 mg, 0.35 mmol) as a ring-opening metathesis polymerization catalyst. The reaction was carried out for 30 minutes. Thereafter, butylaldehyde (108 mg, 1.50 mmol) was added, the mixture was stirred for 1 hour, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, filtered, washed with methanol, and dried in vacuo to obtain 6.66 g of the ring-opened metathesis polymer powder.

Thereafter, 6.0 g of this ring-opening metathesis polymer powder was dissolved in THF (250 ml) in a 500 ml autoclave, and dichlorotetrakis (triphenylphosphine) ruthenium (36.6 mg, 0.03 mmol) prepared in advance as a hydrogenation catalyst. And THF (250 mL) solution of triethylamine (10.1 mg, 0.10 mmol) were added thereto, followed by hydrogenation at a hydrogen pressure of 9.0 MPa and a temperature of 100 ° C. for 16 hours, and then the temperature was returned to room temperature to release hydrogen gas. I was. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, and then separated by filtration, followed by vacuum drying to obtain 5.4 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 26,900, and Mw / Mn was 1.06. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 30/70.

Example 23

In a 1000 ml autoclave equipped with a magnetic stirrer under nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (18.26 g, 120.0 mmol) and 8-tert as cyclic olefin monomers Butoxycarbonyltetracyclo [4.4.0.12, 5.17, 10] -3-dodecene (31.24 g, 120.0 mmol) was dissolved in tetrahydrofuran (550 mL). 1,5-hexadiene (1.6 ml, 14.0 mmol) as a chain transfer agent and Mo (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC (CF ₃ ) as a ring-opening metathesis polymerization catalyst. ) ₂ Me) ₂ (950 mg, 1.20 mmol) was added and reacted at room temperature for 2 hours. Thereafter, butylaldehyde (433 mg, 6.0 mmol) was added, the mixture was stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing and vacuum drying to obtain 44.4 g of the ring-opening metathesis polymer powder.

Subsequently, 40.0 g of this ring-opening metathesis polymer powder was dissolved in THF (400 ml) in a 1000 ml autoclave, and chlorohydrylcarbonyltris (triphenylphosphine) ruthenium (20 mg, prepared in advance as a hydrogenation catalyst). 0.02 mmol) of THF (40 ml) was added, and hydrogenated at a hydrogen pressure of 6.0 MPa at a temperature of 100 ° C. for 20 hours, and then the temperature was returned to room temperature to release hydrogen gas. The ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, separated by filtration, and dried in vacuo to obtain 37.9 g of a white powder-opened metathesis polymer hydrogenated additive. . The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 80.90, and Mw / Mn was 1.36. Moreover, the composition ratio of the structural unit [B] / [E] of the obtained polymer was 50/50.

Example 24

20.0 g of the ring-opened metathesis polymer hydrogenated additive obtained in Example 23 was added to a 2000 ml eggplant flask in 1000 ml of toluene of 5.0 ml of trifluoroacetic acid, stirred at 70 ° C. for 3 hours, and the solvent was distilled off. The resultant was dissolved in THF, added to methanol, precipitated, filtered, and dried in vacuo to obtain 18.4 g of a ring-opened metathesis polymer hydrogenated product which was partially esterified in the form of a white powder. The composition ratio of the structural unit [B] / [D] / [E] of the obtained polymer was 50/13/37, the number average molecular weight Mn measured by GPC was 8040, and Mw / Mn was 1.36.

Example 25

Under a nitrogen atmosphere, 3,6-epoxy-1,2,3,6-tetrahydrodimethylphthalide (21.62 g, 120.0 mmol) and 6,6 were used as a cyclic olefin monomer in a 1000 ml autoclave equipped with a magnetic stirrer. -Dimethyl-5-oxapentacyclo [7.4.0.0 ^3.7 .1 ^2.8 .1 ^10.13 ] -pentadec-11-en-4-one (29.32 g, 120.0 mmol) was dissolved in tetrahydrofuran (550 mL). 1,5-hexadiene (1.6 ml, 14.0 mmol) as a chain transfer agent and Mo (N-2,6-iPr ₂ C ₆ H ₃ ) (CHCMe ₃ ) (OC (CF ₃ ) as a ring-opening metathesis polymerization catalyst. ) ₂ Me) ₂ (950 mg, 1.20 mmol) was added thereto and reacted at room temperature for 2 hours under stirring. Thereafter, butylaldehyde (433 mg, 6.0 mmol) was added, the mixture was stirred for 30 minutes, and the reaction was stopped.

The ring-opening metathesis polymer solution was added to methanol to precipitate the ring-opening metathesis polymer, followed by filtration, methanol washing, and vacuum drying to obtain 47.7 g of the ring-opening metathesis polymer powder.

Then, 40.0 g of this ring-opening metathesis polymer powder was dissolved in THF (400 mL) in a 1000 mL autoclave. As a hydrogenation catalyst, a THF (40 mL) solution of chlorohydridecarbonyltris (triphenylphosphine) ruthenium (20 mg, 0.02 mmol) prepared in advance was added thereto, followed by hydrogenation at a hydrogen pressure of 6.0 MPa at a temperature of 100 ° C. for 20 hours. After the reaction was performed, the temperature was returned to room temperature to release hydrogen gas. This ring-opening metathesis polymer hydrogenated solution was added to methanol to precipitate the ring-opened metathesis polymer hydrogenated additive, and vacuum-dried after separation by filtration to obtain 36.4 g of a white powder-opened metathesis polymer hydrogenated additive. The hydrogenation rate calculated by <^1> H-NMR of the obtained ring-opened metathesis polymer hydrogenated additive was 100%, the number average molecular weight Mn of polystyrene standard conversion measured by GPC was 7940, and Mw / Mn was 1.31. Moreover, the composition ratio of the structural unit [B] / [B] 'of the obtained polymer was 50/50.

Next, the effect when using the ring-opening metathesis polymer hydrogenated additive (Polymer 1 to 24) of this invention as a resist material is shown by a reference example.

[Reference Example I]

About the resist material of this invention, the resolution in KrF excimer laser exposure was evaluated.

[Reference Examples I-1 to 12] Evaluation of Resolution of Resist

The polymer represented by the above formula (Polymer 1, 2) as a base resin, the acid generator (PAG 1, 2) represented by the following formula, the dissolution control agent (DRR1-4) represented by the following formula, a basic compound, In the molecule | numerator represented by a following formula, the compound (ACC1, 2) which has group represented by -C-COOH, and a solvent were mixed by the composition shown in Table 1. Next, they were filtered through a Teflon filter (diameter: 0.2 mu m) to obtain a resist material:

.

The resist liquid was spun onto a silicon wafer coated with an antireflection film (DUV 30, 55 nm manufactured by Nissan Kagaku Co., Ltd., Japan), and subjected to heat treatment for 130 ° C. for 90 seconds to form a resist film having a thickness of 485 nm. This was exposed using a KrF excimer laser stepper (NA = 0.5, manufactured by Nikon Corporation), subjected to a heat treatment for 110 ° C. for 90 seconds, and then padded for 60 seconds using a 2.38% aqueous tetramethylammonium hydroxide solution. The development was carried out to form a 1: 1 line and space pattern. The developed wafer was cut, the cut section was observed by SEM (scanning electron microscope), and the exposure amount (optimal exposure amount = Eop, mJ / cm 2) which resolved the line and space of 0.30 탆 1: 1. The minimum line width (mu m) of the line and space separated by was evaluated to obtain the resolution of the resist. The shape of the pattern at that time was classified into one of a rectangle, a round head, a T-top, a forward taper, and an inverse taper.

Table 1 shows the composition and evaluation results of each register. In addition, in Table 1, a solvent and a basic compound are as follows. In addition, the solvent used the thing containing 0.05 weight% of all FC-430 (made by Sumitomo 3M Japan).

Reference Example Resin (part) Acid generator (part) Solvent Control Agent (part) Basic compound (part) Solvent (part) Optimum exposure amount (mJ / ㎠) Resolution (μm) shape Ⅰ-1 Polymer1 (80) PAG 1 (1) TBA (0.078) CyHO (640) 17.0 0.24 Rectangle Ⅰ-2 Polymer2 (80) PAG 1 (1) TBA (0.078) CyHO (640) 18.5 0.24 Rectangle Ⅰ-3 Polymer1 (80) PAG 2 (1) TBA (0.078) CyHO (640) 17.5 0.24 Rectangle Ⅰ-4 Polymer1 (80) PAG 2 (1) TEA (0.063) CyHO (640) 18.0 0.22 Rectangle Ⅰ-5 Polymer1 (80) PAG 2 (1) TMMEA (0.118) CyHO (640) 18.0 0.22 Rectangle Ⅰ-6 Polymer1 (80) PAG 2 (1) TMEMEA (0.173) CyHO (640) 18.5 0.22 Rectangle Ⅰ-7 Polymer1 (70) PAG 2 (1) DRR 1 (10) TEA (0.063) CyHO (640) 15.5 0.24 Rectangle Ⅰ-8 Polymer1 (70) PAG 2 (1) DRR 2 (10) TEA (0.063) CyHO (640) 16.0 0.24 Rectangle 1-9 Polymer1 (70) PAG 2 (1) DRR 3 (10) TEA (0.063) CyHO (640) 18.5 0.24 Rectangle Ⅰ-10 Polymer1 (70) PAG 2 (1) DRR 4 (10) TEA (0.063) CyHO (640) 17.0 0.22 Rectangle Ⅰ-11 Polymer1 (80) PAG 2 (1) ACC 1 (4) TEA (0.063) CyHO (640) 16.5 0.24 Rectangle Ⅰ-12 Polymer1 (80) PAG 2 (1) ACC 2 (4) TEA (0.063) CyHO (640) 17.0 0.24 Rectangle

CyHO: cyclohexanone

TBA: tributylamine

TEA: Triethanolamine

TMMEA: Trismethoxymethoxyethylamine

TMEMEA: trismethoxyethoxymethoxyethylamine

From the results in Table 1, it was confirmed that the resist material of the present invention has high sensitivity and high resolution in KrF excimer laser exposure.

Reference Example II

About the resist material of this invention, the resolution in KrF excimer laser exposure was evaluated.

[Reference Examples II-1 to 12] Evaluation of Resolution of Resist

In the same manner as above, a resist material was prepared in the composition shown in Table 2.

The resist liquid was spun onto a silicon wafer coated with an antireflection film (ARC-25, 77 nm manufactured by Nissan Nippon Kagaku Co., Ltd.) and subjected to heat treatment for 130 ° C. for 90 seconds to form a resist film having a thickness of 375 nm. This was exposed using a KrF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.55) and subjected to a heat treatment for 110 ° C. for 90 seconds, followed by a paddle for 60 seconds using a 2.38% aqueous tetramethylammonium hydroxide solution. The development was carried out to form a 1: 1 line and space pattern. The developer wafer is cut, the cut section is observed by SEM (scanning electron microscope), and the exposure amount (optimal exposure amount = Eop, mJ / cm 2) that resolves the line-and-space of 0.25 占 퐉 to 1: 1. The minimum line width (mu m) of the line and space separated by was evaluated to obtain the resolution of the resist. In addition, the shape of the pattern at that time was classified into one of a rectangle, a round head, a T-top, a forward taper, and an inverse taper.

The composition and evaluation results of each resist are shown in Table 2 (ie, Tables 2a and 2b). In addition, in Table 2, a solvent and a basic compound are as follows. In addition, the solvent used the thing containing 0.01 weight% of FC-430 (made by Sumitomo 3M Japan).

Reference Example Resin (part) Acid generator (part) Basic compound (part) Solvent (part) Optimum exposure amount (mJ / ㎠) Resolution (μm) shape II-1 Polymer1 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 19.0 0.19 Rectangle II-2 Polymer2 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 20.0 0.18 Rectangle II-3 Polymer3 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 24.0 0.21 Rectangle II-4 Polymer4 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 18.0 0.18 Rectangle II-5 Polymer5 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 17.0 0.18 Rectangle II-6 Polymer6 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 15.0 0.17 Rectangle II-7 Polymer7 (70) PAG 2 (1) TMMEA (0.236) CyHO (640) 19.0 0.18 Slightly T-top II-8 Polymer8 (70) PAG 2 (1) TMMEA (0.236) CyHO (640) 16.0 0.17 Rectangle II-9 Polymer9 (70) PAG 2 (1) TMMEA (0.236) CyHO (640) 15.0 0.17 Rectangle II-10 Polymer10 (70) PAG 2 (1) TMMEA (0.236) CyHO (640) 18.0 0.17 Rectangle II-11 Polymer11 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 20.0 0.19 Rectangle II-12 Polymer12 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 18.0 0.18 Rectangle II-13 Polymer13 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 16.0 0.17 Rectangle

Reference Example Resin (part) Acid generator (part) Basic compound (part) Solvent (part) Optimum exposure amount (mJ / ㎠) Resolution (μm) shape II-14 Polymer14 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 14.0 0.18 Slightly round hair II-15 Polymer15 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 13.0 0.18 Slightly round hair II-16 Polymer16 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 14.0 0.18 Rectangle II-17 Polymer17 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 17.0 0.19 Rectangle II-18 Polymer18 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 19.0 0.18 Rectangle II-19 Polymer19 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 17.0 0.18 Rectangle II-20 Polymer20 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 18.0 0.20 Rectangle II-21 Polymer21 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 18.0 0.20 Rectangle II-22 Polymer22 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 17.0 0.19 Rectangle II-23 Polymer23 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 24.0 0.21 Slightly T-top II-24 Polymer24 (80) PAG 2 (1) TMMEA (0.236) CyHO (640) 23.0 0.21 Slightly T-top

CyHO: cyclohexanone

TEMMEA: trismethoxymethoxyethylamine

From the results in Table 2, it was confirmed that the resist material of the present invention was high sensitivity and high resolution in ArF excimer laser exposure.

As described above, the ring-opening metathesis polymer hydrogenated additive of the present invention and its production method are industrially very suitable polymers for photoresist for semiconductor microfabrication using ultraviolet rays or far ultraviolet rays, which are excellent in heat resistance, decomposition resistance, light transmittance, and the like. It is worth it.

Claims (25)

General formula [1]: [Comment wherein, R ¹ ~R ⁴ wherein at least one of the general formula [2]: (Wherein, the chain line represents a bonding element. R ⁵ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms. Or a straight, branched or cyclic acyl group having 1 to 10 carbon atoms R ⁶ represents a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms W ¹ represents a single bond or 1 carbon atom; Z represents a (k + 2) valent hydrocarbon group of 10. Z represents a divalent hydrocarbon group of 2 to 15 carbon atoms, and forms a monocyclic or temporary exchange with the carbon atoms to be bonded. 1) is a functional group having a tertiary ester group of cyclic alkyl, and each of R ¹ to R ⁴ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, Halogen, C1-C20 straight chain, minute A linear or cyclic halogenated alkyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a straight or branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a straight chain having 2 to 20 carbon atoms , Branched or cyclic alkylcarbonyloxy group, C6-C20 arylcarbonyloxy group, C1-C20 linear, branched or cyclic alkylsulfonyloxy group, C6-C20 allylsulfo A phenyloxy group, a straight, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and X ¹ is -O- or —CR ⁷ ₂ — (R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.) And may be the same or different. j represents the integer of 0 or 1-3.] The structural unit [A] represented by] is contained as needed, and following General formula [3]: (In the formula, R ⁸ ~R ¹¹ are, each independently, a hydrogen atom or a linear of 1 to 10 carbon atoms, an alkyl group of branch-like or ring-shaped, X ² is -O- or -CR ¹² ₂ - (R ¹² Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.) And may be the same or different. M represents an integer of 0 or 1 to 3.) and the structural unit [B] and / Or the following general formula [4]: [Wherein, R ¹³ ~R ¹⁶ is each independently a hydrogen atom or a linear 1 to 10 carbon atoms, an alkyl group of branch-like or ring-shaped, X ³ is -O- or -CR ¹⁷ ₂ - (R ¹⁷ is Hydrogen atom or a C1-C10 linear or branched alkyl group.), And may be the same or different. One of Y ¹ and Y ² is — (C = 0) and the other is —CR ¹⁸ ₂ — (R ¹⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.). n represents 0 or an integer of 1 to 3; and at least the structural unit [C] represented by In addition, X ¹ of structural unit [A] represented by general formula [1], X ² of structural unit [B] represented by general formula [3], and X of structural unit [C] represented by general formula [4] At least one of ³ is -O-, The structural molar ratios [A] / ([B] and [C]) are 0/100 to 99/1, and the ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn is 1.0 to 2.0. Ring-opening metathesis polymer hydrogen additive characterized in that. The molar ratio of the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3], and the structural unit [C] represented by the general formula [4]. ([A] / ([B] and [C])) is 25/75 to 90/10, ring-opening metathesis polymer hydrogenated additive. The molar ratio of the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3], and the structural unit [C] represented by the general formula [4]. ([A] / ([B] and [C])) is 30/70 to 85/15, ring-opening metathesis polymer hydrogenated additive. The structural unit represented by general formula [1] according to claim 1, wherein X ¹ of structural unit [A] represented by general formula [1], X ² of structural unit [B] represented by general formula [3] and general formula [4] A ring-opening metathesis polymer hydrogenated additive, wherein at least one of X ³ in [C] is —O—, and the others are —CH ₂ —. The functional group having a tertiary ester group of cyclic alkyl represented by general formula [2] according to claim 1, which is selected as at least one of R ¹ to R ⁴ in general formula [1]. A ring-opening metathesis polymer hydrogenated additive, which is 1-alkylcyclopentyl ester, 1-alkyl norbornyl ester or 2-alkyl-2-adamantyl ester. The ring-opening metathesis polymer hydrogenated product according to claim 1, which is a single bond of W ¹ of the general formula [2]. A compound according to claim 1, wherein [In formula, at least one of R <^19> -R <^22> is following General formula [6]. (Wherein the chain line represents a bonding element. R ²³ represents a hydrogen atom, a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight-chain, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms, Or a straight, branched or cyclic acyl group having 1 to 10 carbon atoms, W ² represents a single bond or a (k + 2) valent hydrocarbon group having 1 to 10 carbon atoms, q is 0 or 1. And other R ¹⁹ to R ²² are each independently a hydrogen atom, a straight chain having 1 to 20 carbon atoms, a branched or cyclic alkyl group, halogen, or a straight chain having 1 to 20 carbon atoms, Branched or cyclic halogenated alkyl group, straight chain of 1 to 20 carbon atoms, branched or cyclic alkoxy group, straight chain of 2 to 20 carbon atoms, branched or cyclic alkoxyalkyl group, straight chain of 2 to 20 carbon atoms , Branch shape Or a cyclic alkylcarbonyloxy group, a C6-C20 arylcarbonyloxy group, a C1-C20 linear, branched or cyclic alkylsulfonyloxy group, a C6-C20 anisulfonyloxy group, Is selected from a straight, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, X ⁴ is -O- or -CR ²⁴ _2- (R ²⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms) and may be the same or different. p is a ring-opening metathesis polymer hydrogenated additive, characterized in that it further contains, if necessary, the structural unit [D] represented by 0 or an integer of 1 to 3]. The structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3], and the structural unit [C] and the general formula represented by the general formula [4]. Ring-opening metathesis polymer hydrogen characterized in that the structural molar ratio ([A] + [B] + [C]) / [D] to the structural unit [D] represented by [5] is 100/0 to 20/80. additive. The ring-opening metathesis polymer hydrogenated additive according to claim 7, wherein X ⁴ of the general formula [5] is -O- or -CH _2- . 8. The ring-opening metathesis polymer hydrogenated product according to claim 7, wherein W ² of the general formula [6] is a single bond. A compound according to claim 1, wherein [In formula, at least one of R ²⁵ -R ²⁸ is the following general formula [8]: (Wherein, the chain line represents a bonding element. R ²⁹ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms). Or a straight, branched or cyclic acyl group having 1 to 10 carbon atoms, R ³⁰ represents a straight or branched alkyl group having 1 to 10 carbon atoms, a straight, branched or cyclic shape having 2 to 10 carbon atoms; An alkoxyalkyl group, a linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, W ³ represents a single bond or a (k + 2) valent hydrocarbon group having 1 to 10 carbon atoms, s is 0 or And R ²⁵ to R ²⁸ each independently represent a hydrogen atom, a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, halogen, and 1 to 1 carbon atoms. 20 straight chains A branched, branched or cyclic halogenated alkyl group, a straight chain having 1 to 20 carbon atoms, a branched or cyclic alkoxy group, a straight chain having 2 to 20 carbon atoms, a branched or cyclic alkoxyalkyl group, having 2 to 20 carbon atoms Linear, branched or cyclic alkylcarbonyloxy groups, arylcarbonyloxy groups having 6 to 20 carbon atoms, linear, branched or cyclic alkylsulfonyloxy groups having 1 to 20 carbon atoms, and having 6 to 20 carbon atoms An allylsulfonyloxy group, a straight, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a straight, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms; X ⁵ is -O- or -CR ³¹ ₂ - (. R ³¹ represents an alkyl group linear or branched shape a hydrogen atom or 1 to 10 carbon atoms), and may be the same or different. r represents an integer of 0 or 1 to 3. A ring-opening metathesis polymer hydrogenated additive further comprising, as necessary, a structural unit [E]. The structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3], and the structural unit [C] and the general formula represented by the general formula [4]. Ring-opening metathesis polymer hydrogen characterized in that the structural molar ratio ([A] + [B] + [C]) / [E] to the structural unit [E] represented by [7] is 100/0 to 40/60. additive. The ring-opening metathesis polymer hydrogenated product according to Claim 11, wherein X ⁵ in General Formula [7] is —O— or —CH ₂ —. 12. The ring-opening metathesis polymer hydrogenated product according to claim 11, wherein W ³ of the general formula [7] is a single bond. The ring-opening metathesis polymer hydrogenated additive according to claim 11, wherein the number average molecular weight of polystyrene conversion measured by GPC is 500 to 20,000. A compound according to claim 1, wherein In the formula, R ¹ to R ⁴ , X ¹ and j are the same as the definitions in the general formula [1] of claim 1, and the cyclic olefin monomer represented by the following general formula [10]: (Wherein R ⁸ to R ¹¹ , X ² and m are the same as defined in the general formula [3] of claim 1) and the cyclic olefin monomer represented by the general formula [11]: A process of using at least a cyclic olefin monomer represented by (wherein, R ¹³ to R ¹⁶ , X ³ , Y ¹ , Y ² and n are the same as the definitions in the general formula [4] of claim 1); Polymerizing these monomers with a ring-opening metathesis catalyst, and hydrogenating the obtained polymer under a hydrogenation catalyst, In addition, the ring-opening method for producing a meta three sheath polymer hydrogenation product, characterized in that the general formula [9] in the X ^1, represented by the general formula [10] X ^2, and general formula [11] at least one of X ³ is -O-. The injection molar ratio according to claim 16, wherein the molar ratio of the cyclic olefin monomer represented by the general formula [9], the cyclic olefin monomer represented by the general formula [10] and the cyclic olefin monomer represented by the general formula [11] is It is 0/100-99/1, The manufacturing method of the ring-opened metathesis polymer hydrogenated substance. The injection molar ratio according to claim 16, wherein the molar ratio of the cyclic olefin monomer represented by the general formula [9], the cyclic olefin monomer represented by the general formula [10] and the cyclic olefin monomer represented by the general formula [11] is It is 25/75-90/10, The manufacturing method of the ring-opened metathesis polymer hydrogenated substance. The cyclic olefin monomer according to claim 16, wherein X ¹ of the cyclic olefin monomer represented by the general formula [9], X ² of the cyclic olefin monomer represented by the general formula [10], and the cyclic olefin monomer represented by the general formula [11] At least one of X ³ is -O-, and the other is -CH _2- . The functional group having a tertiary ester group of cyclic alkyl represented by general formula [2] selected from at least one of R ¹ to R ⁴ in general formula [9] is 1-alkylcyclopentyl ester, It is an alkyl norbornyl ester or 2-alkyl-2-adamantyl ester, The manufacturing method of the ring-opened metathesis polymer hydrogenated substance characterized by the above-mentioned. The method for producing a ring-opening metathesis polymer hydrogenated product according to claim 16, wherein after hydrogenation, at least a part of the tertiary ester group of the cyclic alkyl in the general formula [2] is decomposed to a carboxylic acid group. 17. The compound of claim 16 further comprising the following general formula [12]: (Wherein R²⁵-R²⁸, X⁵And r is the same as the definition in the general formula [7] of claim 11). A method for producing a ring-opening methesis polymer hydrogenated additive using a cyclic olefin monomer represented by claim 11). 23. The method for producing a ring-opening metathesis polymer hydrogenated product according to claim 22, wherein after hydrogenation, at least a part of the ester group is decomposed to a carboxylic acid group. 17. The method of claim 16, wherein the ring-opening metathesis catalyst is a living ring-opening metathesis catalyst. 17. The method of claim 16, wherein the polymerization is carried out with a living ring-opening metathesis catalyst in the presence of an olefin or diene.